Depending on when you're going, I have the times guide through next week.
Rapunzel is usually 11-5 everyday, and it's best to get there around 10:30. Unless it's a Tue or Wed, the wait is usually never below 45-60 min. I caught it on a Wed afternoon at around 15 min, but I consider that good luck.
Pooh and friends run from 10:30 or so until 4:30-5, depending on the day. The wait is never more than 20-30 min here.
Pixie Hollow is never more than 20-30 min and the CM at the bottom can tell you who is currently there or about to come. That's how I got to see Fawn, as I was told by a very helpful CM, who allowed me to get to the front of the line and then hang out as she was running behind.
Princess Fantasy Faire is great to hit on the mornings that the park opens at 9am. Everyone rushes for the rides and forgets about it. I got in at opening yesterday, strolled by the subs and then made my (long) way over, and was still the 3rd person in line.
Other characters:
Main St: Fab five, Chip & Dale, Pinnochio, Gepetto, Cruella. Yesterday, I caught Mickey, Minnie, Pluto, Donald, Goofy, Chip & Dale all out at the same time around 2:30. They spread out around Town Square form their own lines, or pair off. Just hop into any line you want. Sometimes they overlap or run away into each other's lines.
Beside Pixie Hollow: Captain Hook, Peter Pan, Ariel, Mad Hatter, Alice, Queen of Hearts
Paths beside Castle: Snow White, Evil Queen, Ariel, Cinderella, Fairy Godmother, Mary Poppins & Bert, sometimes Belle, Aurora
On the steps beside Small World: Donald, Chip & Dale, Pooh
Toon Town: Daisy
By Big Thunder BBQ: Jessie, Woody
NOS: Tiana, Naveen (currently)
Adventureland: Aladdin and Jasmine
DCA: Sulley, Jake (Neverland Pirates), Handy Manny, Minnie, Pluto, Duffy, Goofy, Woody, Jessie, Buzz
Keep in mind this was just in one day. You can easily see all these in one day and yesterday there were so many out it was ridiculous!