Personally, I love playing with PoV. It's one of my favorite things about writing. I'd probably write my novels from a dozen different PoV's if I didn't restrain myself.
In all seriousness, I have seen many an author throw in another character's PoV half-way through the story and it works, as long as their PoV is relevant and there was more than one PoV to begin with. For instance, if we go through a novel from Amy's PoV, then 3/4 of the way through, John's PoV comes in, that's a bit off-putting. The reader has experienced nothing but Amy until this point, so why change it? But, if we change things so we're in Amy's and Nick's PoV throughout the story, John's sudden intrusion doesn't seem so bad anymore.
As far as deciding what PoV to do per chapter, I have (quite recently) learned that it's best to go with whatever character has the most to lose. If Amy's mother is dying, it's probably not a good idea to do that scene from Nick's PoV. The reader gains nothing from seeing through his eyes. Oh, but wait! What if Nick is the one who killed Amy's mother? Now it could be worthwhile for readers to see through his eyes. Just depends on which character has the most invested into whatever scene you're writing.
One other thing. If this is a new character, it's best to reveal or hint at a connection between this character and the others that you've been writing about fairly early on. Then it's easy for the reader to care (if indirectly) about this new person that intruded on their perfectly good PoV.
Hope this helped. 