No and the reason why is that the tie is UV Mapped to the rest of the clothing items. It does not have a map of its.

As far as I know, there is no way to mask an area of a UVmap from being painted or have individual areas of a map painted in SFM proper. Not without making many many copies of a texture and paint the area then give that area a black layer mask to keep it from being painted when adding material overrides.

Hey, I got one more question (sorry to bother you btw) is there a way to paint the tie by itself? because when I change spy's suit color, the tie changes with it.