Goofy's opens at 7:00 a.m. every day, and truthfully, on the last couple of visits to DLR, we were there at either 7:00 a.m. on the dot or at 7:30 a.m. Prior to that we would get there closer to maybe 8:30 or so. Chances are, when you arrive at Goofy's - if you arrive at 7:00 a.m. - there will only be Goofy and possibly one other character there at opening. When we walked in, Goofy and Baloo were standing by the entrance, watching us enter, kind of leaning on a wall, trying to size up the weekend morning crowd. So we got to our table and my friend instantly headed to the buffet while I got my camera out and set it on the table to be prepared. I waited for her. As soon as she returned and I got up to get my food, however, some character or other showed up at our table while I was gone and I missed him.

My friend told him someone was missing and to please some back later, which he thankfully did. Anyway, as the morning wore on (in the 90 minutes we were there), more characters began to arrive, such as regulars Chip, Dale and Pluto (he stands at the entry to Goofy's, taking photos with either your camera or PhotoPass cameras) and Aurora, Prince Philip and Jasmine. But they were not all there at 7:00 a.m. They seemed to trickle in over time.
So, knowing that many folks are used to the mass quantities of characters at Minnie & Friends and that Goofy's tends to get a bad rap for 'not having enough characters,' I now try to remember to put out the disclaimer that there may be characters at 7:00 a.m., but the bulk of them probably do not show up until 8:00 a.m., and hang around for a good 2 or 3 hours. I don't mind as much if we get there while the characters arrive over the course of our 90 minutes, because it gives me a chance to eat my food, but I know other folks do mind, so I like to forewarn everyone now! So you can go at 7:00 a.m. but just be aware that only a couple might be there then and the rest will show up as the morning unfolds. The food is hot and fresh at that time, the fruit is juicy and ripe, and the restaurant is not all that crowded right at 7:00 a.m., so I like it, even if we only see Goofy and Baloo or one of the Chipmunks for the first 30 minutes. They tend to come back to the table repeatedly when the restaurant is slower and they have fewer folks to visit, so you get more one-on-one time (my friend was sick of Chip and Dale and Goofy after a while because they kept coming back to our table before Aurora & Jasmine, etc., showed up).
As for Blue Bayou, I would say if you can't make it there at the early 11:30 a.m. seating, then the earlier in the evening, the better. When we were at BB last year at around 8:00 or 8:30 p.m. (I am blanking out on the exact time now), we had to wait at least 45 minutes for a table, and the parlor waiting area was jam packed and HOT. I have a hunch that it gets more crowded as the night wears on. So 5:00 or 5:30 p.m. would probably be good.