Mail.app -- confused between SMTP servers?

BACKGROUND: I have used Terminal for over 10 years to access a Unix server where I get my mail using Pine / Alpine --simple text email and trouble-free wherever I am. Recently my university has been shutting down the Unix server and moving accounts to a so-called Exchange (I know, bad decision!). I'm told that soon there will be no Terminal access, no Pine. Long story short: I started adopting Mail.app. Now, it happens that when I'm home my home smtp server is one, and when I'm at the university it's another (and I assume it's like that wherever I go with my laptop--that's a nightmare; I'll miss Terminal/Pine). I also have a @me.com account running together with my university email in Mail.app. And @me has its own smtp server.
PROBLEM: Very often, when I get home, the home smtp server 'thinks' I'm trying to send university email with the 'me' smtp instead of the internet provider smtp. Also, often the internet provider's smtp rejects university emails because it appears to be from me.com. I keep getting a msg to select smtp servers for every email I send, no matter which account. Mail.app always pairs the wrong email address / smtp server. After about a dozen "select this server" attempts, the msg leaves the Outbox!
QUESTIONS: Is there a way for the smtp server to be selected automatically? I assume it should be like that (I did configure the list of smtp servers and email addresses correctly; so the confusion appers to be in a configuration file, I don't know. Also the connection doctor and the list of smtp servers appear to be correct). Is this a bug in Mail.app?
A more general question: Does this all (see Background, above) mean that I won't have access to IMAP accounts if, say, I'm at a cafe--unless I know which smtp server that cafe uses?? Does anybody know if new versions of Alpine/ReAlpine work in Lion? I haven't upgraded just because of that!

It's in Tiger, sort of, as a drop-down menu in the new message composition window -- requires a one-time setup then it's there for all time.
Click on "compose new message" button in Mail toolbar or type an "apple-n". In message header there is a small rectangular box with 3 horz lines & downward pointing triangle. Click on that box. Select "Customize..." then check the "Account" checkbox, and in the future you will have an "Account" drop-down menu in the header area of your new message composition windows that will select what account to apparently send from (which selects what smtp server to use). It uses whatever email address belongs to that account for the "From:" address, though -- probably not exactly what you want.

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