Derek Sivers wrote an interesting post (http://sivers.org/la) as advice for folks moving to LA. Here's my thoughts on the same topic, but about Baltimore, MD.
I moved into South Baltimore in 1996 and I've lived in this neighborhood ever since. Here are a few of my thoughts (please fork and edit):
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Baltimore is made up of many different neighborhoods. Getting to know the character of each of the them will enhance your experience. Visiting the baseball stadium and going to dinner in the Inner Harbor does not make for a satisfying Baltimore-experience. You have to get it into the neighborhoods to find the truly great food, the fun bars, and genuine people.
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"The Wire" is real, but you probably won't see it. Unless you're visiting your cousin who lives on West Lanvalle, you probably won't see much that resembles a Barksdale corner. And don't ask for a "Wire Tour" - that's not what we're about.
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People are friendly, especially the older folks. If you have a chance, take a pause to listen to their story, or hear about what it was like "in the old days". Baltimore is a fascinating place, in that so many residents have lived here all their life.
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Public transportation is not that great, so be prepared to drive and walk. Parking in busy neighborhoods can get pretty bad, especially at night. Moving to the city? Try to live where you can bike to your destinations.
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Visit DC. Visit Philly. Visit NYC. Go to the beach. Have a weekend in the mountains. Especially if you're not from the east coast. These things are so close around here, so take advantage of the proximity.
off the top of my head I would also mention: BOLT bus, supportive DIY culture (lots of successful people around who will help you, attend your happening, etc), the fact that the city has a bit of a "middle child" syndrome in that it's always trying to promote itself in embaraasing ways (like weird slogans), the politics are baroque and strange because we have an old-fashioned Democratic machine, it's laid back and people don't care so much what you do for work