Not sure how it works in Outlook Express because its a buggy peace of cloogey crap that even MS doesn't want people using. With the full Outlook app, you can have the email accounts setup based on who is logged into the machine.
Also, if you have the two email addresses, and neither person is supposed to be seeing both, only setup the address that they are supposed to see. When someone logs in, the emails will get downloaded to whoever accesses the server first (ie - the first logged on user). If they can't see the other account, they can't download from that account.
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