The question is: what is a bigger boost: Castro's boost to Hispanic vote or Kaine's boost to VA?
While I wouldn't say Kaine guarantees Virginia, but he probably assures a small, but significant bump. I also think Kaine plays decently in the Midwest, which is where Republicans would likely look to make up Electoral Votes. He's also smart, competent, and a nice guy.
Seeing as the Hispanic vote is fairly concentrated in both Texas and California, I'm not sure Castro would really boost the ticket in terms of Electoral Votes.