There's a workflow hack or two to ensure that novel transactions get checked by me, eventually. (e.g. I have a personal credit card in the mix, for those rare times when both business cards fail, which means she sees a lot of transactions which aren't business related and should filter them all out. It wasn't obvious from the one-line description that e.g. my wedding venue is probably not appropriate for deduction, but since it was marked as novel (and ginormous relative to my expected expenses for that month), I caught it prior to doing the year in review numbers.
I do a more in-deoth review of the big expense categories (AdWords and travel) prior to doing my taxes and spot-check everything else. If e.g. a $60 software purchase ends up getting missed that's unfortunate, but it is only about ~$20 of unfortunate, and a few slip-ups are substantially cheaper in opportunity cost (and sanity) that having me do line-by-line review of all ~500 entries.
For general advice on how to work with VAs, I strongly recommend Rob Walling's book and have heard good things about the 4 Hour Work Week (but have never read it).