What's your mail provider in outlook express? Is it a work email address? Or are you using a free service like yahoo?
First off, I'd recommend not using the stock email app. Use something like K9 Mail or Maildroid, they are less buggy overall, and will give you more flexibility (like being able to automatically bcc yourself on outgoing mail).
Having a copy of incoming mail is simple. She should get it no matter what as, from what I gather, she's using either the website, or the aol program itself. In either of those cases, all email regardless of wherever else it goes is available from there. In your case, you also should be fine, depends on your sync setup in outlook mostly (if it grabs read mail).
The outgoing is tricky, the bcc option always works, but depending on the mail provider it may not be necessary. AOL should show sent items from the phone where it normally shows sent items, as it is a full imap implementation (test it to make sure, obviously). Yours will depend on your mail provider.
To actually set the accounts up, you may get lucky and it will automatically know the settings for the servers you're using, AOL I can pretty much guarantee. That means, your wife can just put in the email address and her password, and it should just work. Yours, again, will depend on your provider. Your settings can be viewed in your mail account settings in outlook express if nothing else.
