Shims can help a decent amount. What you are doing with shims is creating additional thermal barriers for the heat to cross to get to the pistons and ultimately the brake fluid. Its the same concept as putting fiberglass insulation in the walls of your house.
Now, as far as how good Ti is, I dunno, haven't checked the #'s, or actually used Ti shims, but I have used stainless steel shims to good effect.