I have used both products and here is my impression:
Smashbox has virtually no smell. I know it has a lot more extracts in it than the Monistat, but I can't detect the smell. It works VERY well for me as a primer. I use bare escentuals foundation, so the primer eliminates the "powder-on-top-of skin" look for me. I formerly mixed in MAC's Vanilla Pigment in with my moisturizer, but when I started using the primer, I noticed the pigment travelling a bit more than I would have liked, so I started moisturizing first and then applying the primer with the pigment mixed into it which worked VERY nicely.
Monistat has one major difference from Smashbox: it has a petroleum-like smell that might be unpleasant to some. Frankly, I don't care about its smell. Additionally, its texture is quite a bit thicker than the Smashbox. I prefer this thicker texture because for me, it's easier to judge how much product to dispense.
Aside from the price, Monistat has one HUGE advantage over the Smashbox product. PACKAGING!!! Unless you get the Photofinish in the travel-size tube, it comes in a glass pump dispenser bottle. Thus, when you start running low on product, there is about a tablespoon of primer that you will never get to unless you break the glass. Monistat comes in a tube and couldn't be easier to dispense.
ONE THING YOU SHOULD KNOW!!!!
Photofinish primer gained a lot of infamy early on because it has been known to cause severe cystic acne in people with large pores/acne prone skin/very oily skin. For that reason, Smashbox developed a primer for oily skin (for which Monistat has no equal). If you have any of these skin issues, THINK TWICE before getting either of these products.
My winner? Monistat by a landslide. I have no skin problems after using it, and I think a primer is an essential tool for mineral makeup wearers. I love it, I use it, and I'm sorry I dished out the money on the Smashbox in the first place.