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It's easy as hell to hit someone with volley, good lord. Pretty easy to land ult from a safe distance too. A ranged champion with 3 forms of ranged cc is going to have an easy time doing basic kiting.
Vayne is going to be harder because she has a much shorter range. Thus, kiting with Vayne is more about positioning than Ashe and knowledge of who the other character is / what to watch out for. Not only that, her crossbow knockback takes a while to get used to ( this is coming from a person who finds skillshots to be easy ). She's going to be a faster-paced kiter who relies on judgement and reflexes and is in cc range.
A caitlyn player needs to good at skillshots and aggressive behavior or else she won't have a far lead on her opponent. By aggressive, I mean landing headshot-proc'ed hits on champions that are trying to last hit, and consistently hitting the enemy with her skillshot. Though her range and skills allow her to play safe, playing her is not as simple as playing Ashe.
Imo, Ashe is easier to play than Cait, and Cait is easier to play than Vayne.
oh and please fellas, refrain from buying AS items before AD items on ranged carries.