I know how to add a new account in Outlook, but any time I tried it, I wound up with about two or three extra folder sets that I couldn't delete. I absolutely despise Outlook's .pst data file system; I think the feeling's mutual, because every time I try to fiddle around with them, I wind up screwing something or other up and having to muck around for an hour before everything is set right.
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Also, at least to the best of my knowledge, there was no way to get separate accounts to download messages to the same inbox; I may be wrong on this one. I know that there was no drop-down selection menu like Thunderbird uses so that you can select which account you'll be sending the e-mail from; this is one of the features about Thunderbird that struck me immediately. I did finally figure out profiles in Outlook; however, to use them, I'd have to log in under one account, close out, then log back in in another, which was very cumbersome. As for the multiple SMTP accounts, I have two set up right now, even though they're not absolutely necessary, and I've sent out multiple messages without experiencing any problems.