We'll start with the character differentiation bit. There are twelve team captains now (nine regular plus three unlockable), each with pretty amazing super-moves that have a huge effect. Donkey Kong can trigger a huge shock wave that blows defenders away. Peach can do this weird thing where giant Polaroid pictures fall from the sky and trap opponents inside their frames. Luigi has the evil gas we mentioned before. It's big stuff that really affects the gameplay.
Of course, this is still four-on-four soccer, so the team captain is only part of the action. You have eight sidekicks from which to choose: Koopas, Toad, Dry Bones, Boo, Birdo, Hammer Bros, Monty Mole, and Shy Guy, and you can mix and match them however you like. Each has unique powered-up shots of their own as well. For example, Monty has a shot that burrows underground, and Shy Guy can actually ride a giant Bullet Bill into the goal.