But if we're talking about newsletters your don't remember signing up for or marketing emails or invites to a new social network, the unsubscribe usually works and will almost never harm you. AFAIK it's a myth that there's this huge black market for "valid" email addresses. Spammers don't want a list of people who click unsubscribe; they ain't gonna buy anything. There are way easier ways to find email addresses on the internet. And it would be crazy (and possibly illegal) for any sort of semi-legit company to sell their unsubscribe list.
Anything send by an actual company -- especially anything sent through any of the major email providers -- will almost certainly have a working unsubscribe. It's almost impossible to send a message in MailChimp without a working unsubscribe.
I think the fear of "confirming an email address is valid" is unfounded. A list of valid email addresses of people who actively report messages they don't want as spam is not worth anything to a spammer and it would be illegal for a US company to do anything with the list of unsubscribes or spam reports anyway.
I'm not aware of any simple and universal solution to "undo" an accidental spam button click.
[1] http://en.wikipedia.org/wiki/Feedback_loop_(email)