By default we auto-login into the native enterprise store for a better user experience. We verify credentials on every native store opening and on every calls.
However, if you want to logout to select another account here are the steps :
If you use an email and password login
Select your profile
Click on sign out
If you use an SSO login (with your company login)
You should still be able to do the same as for email and password, but some SSO like SAML may have disabled the auto-login after few days, so you will be automatically logged out.
You will have to login again by entering your company credentials, either email or identifier + password.