Gaara - Leader
Former JINCHUURIKI of Shukaku, current Kazekage, has "Love" written in Kanji on forehead, all-around badass. Can serve as a tactician, strategist, scout the area with his eyeball thing. Is also able to be both a must in offensive and defensive. Has a gourd full of sand, and can turn the earth into his own sand, creating various moves such as Sand Tsunami and Sand Burial. Defensive wise, his freaking dead mother protects him and his comrades at all times. Also, he can fly.
Naruto - Fighter
Very flexible in terms of position. Range fighter with Tailed Beast Bomb and RasenShuriken. Very fast in Bijuu Mode. Can also be a sensor during Bijuu Mode, able to sense Light and Dark chakra/intentions/whatever it was called. Due to becoming friends with Kurama, he has a lot more chakra reserve now, he can summon a bajillion Shadow Clones and wear out enemies.
Killer Bee - Fighter #2
The current Jinchuuriki of Gyuki. Basically the same thing as Naruto, but more experienced, and has more knowledge. They can both use TBB to kill a lot more enemies. Is also experienced with with his swords when he has to fight in close-combat.
Tsunade - Medic
The 5th, and so far only female Hokage. Can heal everyone with or without Katsuyu, and is basically unkillable during Mitotic Regeneration. Is also a powerhouse, as shown when she was able to punch and break Madara's Susano'o.
Teamwork.... It depends on what kind enemy they're fighting. Well, whatever the situation, it will probably be something like this: Tsunade summons Katsuyu, and tells her to give them four smaller slugs so they can be healing at all times. Gaara uses his eye to scout the area. Naruto summons clones to fight, while the real Naruto gathers nature chakra for Sage Mode and/or prepare for Bijuu mode. Killer Bee goes with the clones, and fights the enemies. What happens after that, it's all up to your imagination.
As for getting along, of course! Gaara, Tsunade, and Killer Bee are all friends with Naruto. Gaara and Tsunade are together, along with the other 3 Kages, fighting Madara. Only problem is them two not properly knowing who Killer Bee is, but that's ok. They fought alongside his brother, A, so they'll trust him to cooperate with the team.