I've always enjoyed Lloyd Bochner as Mazoor Berozski in "Most Dangerous Match" as he literally pushes Columbo around while yelling at him, "Tell me something, why are you here? You are homicide detective. Nobody has died here. So why don't you go home? Go home, what do you care about garlic? About shirts?" Cracks me up every time.
The one he gives the most reason to blow up at him might be Beth Chadwick, since of course she's already been cleared. Instead, she's pretty restrained. (Maybe it's that "classiness" that he mentions in the final scene.)