Simply smelling good and wearing cologne are different things. Continuing the make-up comparison, what about a woman who wears too much make-up? It creates a different effect than a cologne/perfume, but it's not something that generally makes me think better of a person during a first impression. And yes, as a general rule, I think less of a woman who wears too much make-up.
This isn't some golden rule that I live by, just something that my mind leans towards because of past experiences. I'll restate it more simply: Younger people (sub-40ish) who often wear perfumes to more everyday affairs (work/school/shopping) tend to be the kinds of people I don't get along with because they've often been wannabe big shots. There's several shades of grey in my judgement process and this is just, as you said, another piece of the puzzle.
Most of the people who helped shaped my opinion on the matter are lame punks from California, so a metro like you, Pug, would probably already be exempt from such opinions.