A good way to throw your opponent off guard is to just rush and throw him. If they are quick they can react to it, but if they aren't suspecting it, then there you go. I have been doing that a lot more with other characters. I will do a certain number of moves in a pattern to get my opponent used to it, then I will just run up and throw him to break the cycle.
With smoke players, when I am H. Smoke and they are R. Smoke, I will wait for them to make a move if they are on the other side of the screen in a crouch block, and usually I can wait long enough to make them do something and then I can just slap them with a telepunch.
