It would depend on the time of year you were going. We went in October and met all of them! Well, we skipped the Little Einsteins and the Mickey Friends, but we left the park by early afternoon, so we had plenty of time to meet more if we'd wanted to. We did spend two days at DHS, so the first day was mainly the rides - saw a few characters (which we doubled up on the second day) but some had to leave before we got there, so we spent day 2 on a character hunt. Here was our itinerary for that day:
I was deemed the runner, so at rope drop I went for the Toy Story Mania FP's while DH followed with the boys at a slower pace. He got in line for Woody and Buzz (because it's the only location that features both of them together and because it's across from the biggest family ride at the park, it's a very popular meet 'n' greet!). By the time Woody and Buzz came out (I believe at 9:15) the line is usually an hour long. After getting the FP's I joined my family in line and waited 5 minutes - great interactions with both of them and a lot of fantastic pictures! The line for this one is around a wall, so you can't see what is happening, which means the handlers don't rush people along the way they sometimes do (great for when it's your turn, but it does make for a longer wait time).
After Woody and Buzz we headed down to the back of DHS to see Lightning and Mater - we were the first ones there since everyone was still at the craziness that is
Pixar Place at rope drop. We got a lot of great pictures of all different angles - some with just the kids and some family pics. We even stood and talked to the workers for a few minutes since there was no one else there and they directed us to a spot that was pretty much right next to them and said Phineus and Ferb would be coming out in a few minutes. We were going to skip it since my kids don't watch the show, but the oldest DS decided he wanted to be "First in line" and he still talks about it

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After a few rides, we went over to the Magic of Disney Animation around mid afternoon. Lines were somewhat long, but not horrific. We went to the Incredibles first and it was about a 10 minute wait (no Photopass at this one). Then we went down into the animation area and got pictures with Winnie the Pooh (this one changes - Lotso Bear was there two years ago) - Lotso was short lines, but Winnie the Pooh was a bit longer (about 20 minutes) and then the boys wore me down and we got in line for Sorcerer Mickey. This was one we skipped the previous year, but I caved. It was the longest character wait we had (of any of them) so if I had it to do over again, I would've been in there at the time those characters came out. As it was, I think we waited for 50 minutes - maybe a little more.
After that, we backtracked to Mike and Sully (we got pictures with Mike the previous Day, but Sully had to go take a nap right before we got there). They are somewhat hard to find - I was actually standing right next to the area and didn't realize it earlier in the first day. Make sure you ask a cast member where they are - it's near the Honey I Shrunk the Kids playground, behind a gift shop. This was a short wait for after lunch, considering the popular characters, but since they are so out-of-the-way it was easy.
Good luck! And make sure you get a Times Guide at the front of the park! Woody and Buzz come out early, but the Disney Animation area doesn't open until later in the morning and I don't think Mike and Sully came out until 11:00. My recommendation is to definitely get in line for Buzz and Woody first thing if that is on your list!