Well, I think you can pair them with different personnality traits:
1) Twilight & RD: both are fan of Daring Do ; AJ and Fluttershy: both have a connection nature ; Pink pony and Rarity: both are very good party decorators + tendancies to overreact.
2) Twilight & AJ: both can be rational and down to earth, give good advices ; Fluttershy and Rarity: both know about fashion, are good singers, can be very calm ; Pink Pony with Rainbow Pony: Both are jokesters
3) Twilight & Fluttershy: both can be calm and sensitive ; RD & AJ: both have rugged personnality and enjoy playing games ; Pink Pony and Rarity again.