When choosing a caulk don't go cheap. I recommend getting a top quality siliconized caulk. Don't use a 100% silicone caulk if you are painting because the paint will not adhere if you do. Make sure the caulk is completely dry before you paint or your paint will crack.
Quick Episode Summary:
0:34 Is Your Trim Work Caulked?
1:05 Benefits of Caulking
1:13 Where Should You Caulk
1:23 What Caulk to Use