I have a workaround that seems to do the job.
If the mailbox has an alias address - eg *** Email address is removed for privacy ***, use that address when setting up the mailbox.
If it doesn't already have an alias address, create a new one and then use that address.
This will still link to the mailbox as normal, but will give you the option to log in as a different user.
When sending email, and as far as the folder list goes, everything will behave normally. The only two side effects I've noticed from this is that the OST file will be named after the alias address (which the user will not even be aware of), and when syncing, the status at the bottom of the outlook window will show that it's syncing the alias address as opposed to the actual address - not the end of the world!
Other than those two things, everything else is the same, but it allows you to switch user accounts when logging in.
EDIT - Bah, Microsoft removed the example email address I put in! The example above was emailaddress at companyname dot onmicrosoft dot com