The first Doctor that Madam Vastra encountered was the 9th Doctor during one of his very earliest adventures.
It's been a while since I've seen "The Hungry Earth", but had the Doctor encountered the Vastra breed before that story?
She seems to know about regeneration in Deep Breath.
She gets the Brig's line "here we go again".
She's also aware of regeneration in A Good Man Goes to War, and even knows quite a bit about Time Lord ways, including the Untempered Schism.