"Oily" sounds like it has been used show how the writer feels this smugness is unpleasant, I couldn't say exactly how, but I think it is supposed to create an image. Perhaps, compared to being "brash", this is equally unpleasant but in the way that an unwanted guy trying to talk to a woman at a bar is.
So where "brash" is very obvious and loud, "oily" is more subtle. I'm getting an image of a snake, slithering around. Still unpleasant, but not as obvious as a bear stomping around the place!
Hope this helps!