Don't forget the people that abuse the "mark as spam"-button as unsubscribe link. I saw that beahvior with non-techy users - it's often easier to find than the unsubscribe link and has the same effect to them.
N = 1, but I used to put it in the second sentence of my emails. The unsubscribe rate was still measured in basis points, although I had an unusually high quality list relative to e.g. most e-commerce shops.