ChromeOS developer here (opinions are my own, etc etc), writing as a user though since I don't work on this specific field myself but I've been using chromebooks daily with multiple accounts (corp and personal) daily for the greater part of a decade.
You have a few options on how you log into ChromeOS. Once you boot the device, you can choose which account to sign in as. If it's your corp account, you get whatever corp policies get applied to you (like no play store, no linux, etc). If you log into your personal account, you don't get those restrictions (there's a note to be made here for stuff like enrolled devices which I don't think applies to OP and I'm not too familiar with anyway).
However, once you are already logged into an account on the device, you can also choose to "sign in with another account". This makes you run two accounts at the same time, you can swap between them without using passwords, etc (it's like switching a virtual desktop/workspace). You can even transfer windows from one account to the other so you can simply alt+tab between them as you would on a single account (for example I am typing this at work on my personal account in a window running inside my corp account). In this situation, whichever account logged in first is the account that "owns" the session and has policies applied. If you log into your corp account with play store disabled, and then log into your personal account as a secondary account, you can't use the play store on it. If you log out everything and re-log with your personal account, you will still be able to use the play store there.