Perfume samples are the best way to figure out which scent to purchase. It's best to try the fragrance and see how it works with your body chemistry prior to purchasing the whole bottle.
Ever been blasted with a spritz of discount fragrance while entering a department store at the mall? This doesn't happen that often these days, as many folks are sensitive to certain scents. But, the practice used to be commonplace with overzealous saleswomen.
Another thing you might encounter are people selling discount perfumes in supermarket parking lots. Typically they have a trunk full of various discount fragrance and they will try and get you to try out various different ones in the hopes that you will purchase a bottle or two.
The term may look like a combination of the words "personal fumes" but that's not how it got it's name. It's a derivative of the Latin "per fumus" which translates to through smoke.
When smelling the different types, be sure to clear your palate by sniffing a dish of fresh coffee beans. This will help your nose get ready to smell the next scent without any residual smells from the last scent you sniffed.
When applying the fragrance, put it on your skin - like the inside of your wrist, for instance, and let it sit for awhile. It will tend to smell different on you than it does in the bottle. I heard a morning radio show broadcast recently where a man absolutely loved the scent a co-worker was wearing, so he purchased a bottle and it smelled nothing on him like the scent he so admired on his colleague.
Depending on the type, you may want to try different application techniques. Spraying it into the air and then walking through it, for instance. This is helpful when the product is of a high concentration. This next section explains that a little better:
Parfum or Perfume can have anywhere from 15-40% of the "essential oils" concentrates, making it the longest-lasting and the most expensive.
Eau de Parfum contains less (typically 15%) concentrates and while it's still long-lasting, it can cost considerably less than the really pure stuff.
Eau de Toilette is more of a light scent that's more for freshening up and doesn't last too long.
Eau de Cologne are citrus type scents with 3-8% (average 5%) aromatic compounds.
Here's a listing of resources for where to obtain womens fragrance and perfume samples: