Do both male and female skunks smell?

Yes, both gender of the skunk can spray.

2nd Answer:

I say, from personal experience that skunks of both genders can spray. I stumbled upon a pair of mating skunks (male and female) and upon observing their rituals (sex practices) they became agitated at my close presence. My video camera was probably bothering them - they discontinued skunk coitus and simultaneously sprayed me and my video camera. So, YES, skunks of both genders can spray and I would assume that skunks of mixed gender can also spray.