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A lot of us have to juggle more than one Google account these days, be it for work, school, or personal stuff. On Chrome OS, where user profiles are intertwined with Google accounts, managing those can feel overwhelming, especially since there are multiple ways to tackle the problem: You can create two users for two accounts, add two Google accounts to one user, or build a combination of the two. There are advantages and disadvantages to all of these solutions, so let's dive into what you need to consider for your setup.
First, we should distinguish between Chromebook users and Google accounts — even if the former isn't a term consistently used by Google, they'll make talking about the differences easier. Chromebook users have a dedicated spot on your Chromebook's lockscreen and are based on Google accounts. To start using a Chromebook, you'll first have to create one of these profiles by signing in to your Google account. This will be your owner account. It will always be the user you first created on your Chrome OS machine, and the role can only be changed by a factory reset.
The owner account has some extra permissions and is the only one allowed to manage other users. You can check if your current profile is the owner account by opening the Settings app, going to the People section, and looking for the Manage other people entry. Click it, and you'll see options for enabling guest browsing, restricting sign-in for specific users, and you can choose which information to disclose on the lock screen. If you're not the owner, you'll see a note saying, "These settings may only be modified by the owner."
Options are locked when you're not the owner.
Once you've created your first Chromebook user by signing into your Google account, you'll have access to the same files and data available to you when you use Google Chrome or an Android phone, such as bookmarks, browsing history, passwords, extensions, settings, contacts, emails, and open tabs on your other devices.

One user for multiple accounts

While you need at least one Google account to get your Chromebook up and running, it's still possible to add secondary accounts to your user. To do that, open the Settings app and head to the People section. Click on your profile picture, and you'll find the option to add another account. Once you've done that, the list in that section will be updated to include your other identities.

Advantages

The big advantage here is that it's easy to access your other Google accounts' data. You never need to switch to another Chromebook user, and you won't have to worry about remembering where you saved files or downloads. You also have access to some of the other accounts' data, like its emails, Drive files, contacts, and more. On sites that offer Google sign-ins, you can use your secondary accounts.
Sign in with any of your Google account on web apps.
In Android Google apps, you can switch between multiple accounts by tapping or swiping your profile image. If you purchased apps or subscriptions via your secondary account, it's possible to install and use them on your Chromebook without switching between users.
Switch between accounts in Android apps.
Using one user for two or more Google accounts is additionally less resource-intensive than juggling multiple users concurrently. You don't need to have two browser instances running simultaneously, so you can save some of that precious RAM.

Disadvantages

The most significant disadvantage with this solution is that you don't have access to your secondary accounts' bookmarks, saved passwords, browsing history, or custom search engines. These are only available when you create a new user for each of these accounts.
Similarly, security might be an issue. You won't have separate password protection for each account, so if you forget to lock your Chromebook, an intruder could access all of your Google accounts (and more).
If you have both a personal and a work account, you might also have problems mentally entering leisure mode in your mind due to the lack of boundaries between the two profiles. Your company email and Slack are just a click away, so depending on your mindset, it might be hard to snap out of work mode when you just want to scroll through Twitter or watch Netflix at night. That also works the other way around: With your personal stuff right at your disposal, you might find yourself procrastinating.

Multiple users for multiple accounts

If you want to keep your work life sealed off from personal stuff, you can go another route: Create a secondary user with your work account. Of course, this is also good if you have any other reason to use separate accounts, like when you're a student.
To add a new user, sign out of the session you're currently in and select the Add Person option on the lock screen, which you can find in the bottom left corner next to Shut down and Browse as Guest. Your Chromebook will ask you to sign in via a Google account — just enter your credentials like you usually would. If you've used the Google account in question on Chrome, another Chromebook, or Android before, you'll find browser data like history, extensions, bookmarks, and apps waiting for you.

Multiple sign-in

To switch between your profiles on the fly, use Chrome OS' multiple sign-in feature. It'll allow you to access any signed-in user without requiring a password. You should only do that when you have full control over all of the accounts in question — otherwise, someone else could potentially gain access to all your accounts when they use your Chromebook.
Click your profile icon and you're presented with the option to sign in other users.
To get started with multiple sign-in, click your profile image in the top right corner of the quick settings area and select Sign in another user. Once you've unlocked your other account, you can switch between it and your other one by clicking your profile picture in the aforementioned spot or using Ctrl+Alt+. and Ctrl+Alt+,.
You can also move windows to other users by right-clicking them and selecting Move window to [account]. Just keep in mind that it's an experimental feature and that there might be some problems with notifications or cookies.
If you want to stop using multi sign-in, you'll need to sign out of all accounts and sign back into one only.
Multi sign-in warning.

Advantages

This solution mostly behaves like separate Chrome profiles on a Mac or Windows PC. Each account gets to retain its own bookmarks, tabs, extensions, settings, and more. On Chrome OS, that's also true for files and downloads — if you want to separate those between different accounts, you can easily do that with multiple Chromebook users.
This is also the best method if you want to share your laptop with someone else. Both of you get access to your own data only without having to navigate the other person's data and files (also great if whoever you share your device with is particularly nosy).

Disadvantages

When you use multi sign-in, you can access neither Android and Linux apps nor Google Assistant on the secondary users. If you don't see yourself switching back and forth too often, that won't be a problem, but it's a big limitation to keep in mind when you want to work on both users in parallel.
No Assistant and neither Android nor Linux apps for secondary users on multi-sign in.
Even if you don't use multi sign-in, setting up and managing two users can wind up being less than intuitive and the divide between two profiles might give you headaches. If you'd rather not deal with that, the one-user solution could be better for you.
The advantage of separated files and browser settings can also be seen as a disadvantage, depending on your workflow: You have to remember which files you've downloaded on which user and which apps and bookmarks are available. The separation adds some friction when you just want to look up something real quick.

Combination

It's also possible to combine these approaches. If you have multiple Google accounts for work, you can add them all to a dedicated work user, and if you have more than one personal Google account, you can do the same for your other user.
It's also possible to mix and match by creating two Chrome OS users and adding the same two Google accounts to both. That's handy when you want to synchronize browser history independently when it matters, but you'd still like to be able to access all of your emails and Drive files through both users. This might be the best of both worlds.
Personally, I'm a fan of the one-user solution. I like having all of my stuff instantly accessible and don't want to think about switching profiles just because I'm not sure where I saved some file or which account I used to research some topic. I also like that I can access Linux and Android apps at all times. Other people might prefer having a stricter separation between work and leisure, like AP's own Rita. She's heavily invested into the Ctrl+Alt+. keyboard shortcut to switch between accounts, so the choice between these two methods really comes down to your personal preference.