What type of ceiling: Popcorn? Flat? Slightly Textured? If it's popcorn, painting's a little tricky (pretty much requires a spray gun). Otherwise, go ahead and paint it (first), the end result will look much better.
As for trim, you'll want to paint all the trim and doors with sem-gloss paint (wheras you'll want flat on the walls). You can either match it to the room color or, like we did, pick an accent color for contrast.
Go to your local hardware store, start grabbing fistfulls of paint chips. If you've got anything you know is going in the room (curtains, art work), start seeing what colors go with that. And pick up the myriad brochures that should be sitting on the shelves with the paint chips. They are filled with good examples of what kinds of color combinations work.
Get a good primer, it will make doing the color coat much easier. And if you're painting on a surface that previously had a semi-gloss (the trim, for instance, probably does), be sure to sand that BEFORE you put primer on. And don't bother trying to use the blue tape for edging, more trouble than it's worth. Just take your time, develop a steady hand, and keep a small supply of all paint colors around for touchups.
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'He who receives an idea from me, receives instruction himself without lessening mine; as he who lights his taper at mine, receives light without darkening me.'
-TJ
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