Heres a start if you happen to be using postfix.. but since you didn't specify all I can do is speculate..
http://www.postfix.org/ADDRESS_CLASS...y_domain_class
I don't think a backup mail server typiclaly delivers to mailboxes.. it holds everything in a queue to be forwarded to the final delivery destination when it comes back up.
Most mail clients don't have provisions for multiple servers for a single email address.. I suppose you could configure thunderbird for multiple mail accounts with a single storage location and it would check both servers and download mail from both servers.. the users wouldn't really be able to tell the difference..