So here is the logic:
Vortex has not canonically shown interest in dudes. So he gets first spot.
Stolas has only a little experience being gay. And it is with a imp, which is a very small creature compared to him so he has never had reason to learn.
Sally I have no reasoning for. But I wanted to include her.
Millie and Moxxie both dated Chaz which according to himself(and his visuals) had a biiig schlong. So they both know how to work that pole.
Versosika is literally a succubus.
Queen bee is the SIN OF GLUTTONY. She would NEVER back down on a challenge to stuff her gullet.