I've done a lot of character dining as an adult with no kids, and my picks would be:
Breakfast - Bon Voyage at Trattoria al Forno - Disney's Boardwalk. best food I've ever had at a character breakfast, easily - good interaction with face characters. Plus the Boardwalk area is so lovely in the morning. Characters are Rapunzel, Flynn Rider, Ariel, Prince Eric.
Dinner - Storybook Dining at Artist Point - Disney's Wilderness Lodge. Definitely had the most elegant feel of any character dining I've attended, I think this is as close as you'll get to the ambiance you are looking for. Characters are Snow White, Evil Queen, Dopey and Grumpy.
Runners up:
Tusker House (Mickey, Donald, Daisy, Goofy)
Garden Grill (Mickey, Pluto, Chip, Dale)
1900 Park Fare (Alice, Mary Poppins, Mad Hatter, Pooh, Tigger at Breakfast; Cinderella, Prince Charming, Step Sisters at dinner)
(all serve breakfast AND dinner, although I've only done breakfast at these ones)
I did put up a review of my experience at Storybook Dining - hope you'll find it helpful. Went with a friend (2 grown-ups) last Thursday.