What the original poster is asking for is virtual mailboxes and a back-end for storing user information (other than in /etc/passwd) -- covered at:
http://www.postfix.org/VIRTUAL_README.html#virtual_mailbox
Works great.
I've used that stuff before. Only caveat is that you'd also want to write some kind of front-end to administer the setup including setting up appropriate protections. Especially if you let end users create/edit/delete usernames in your directory or database server setup.
You can use any of the back-ends available for virtual mailbox support -- DBM, MySQL, LDAP, flat files, etc. Pick whichever one you're comfortable with administering.
I would strongly recommend something other than /etc/passwd or flat files. LDAP or MySQL would probably be a better choice since you can enforce more fine-grained permissions for create/edit/delete.
It's better than hacks like filesystem ACLs which would still leave you vulnerable to users touching other domains' users account information.