I don't have a pstv, but to my knowledge you can't change accounts on a regular vita. You'd have to delete the account then add a new one. Hopefully you have better news!
Yes you can have multiple accounts per vita. The downsides to this are that you must have a separate memory card per account, You will only be able to share card based games, and the process of switching accounts is long and cumbersome.
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Topic: PS Account on Vita question
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