We use pretty much all of them. The catalog usually explains what each blend is recommended for, so that's a guideline. If you sign up for their emails, they will send you coupons for free or token-priced small bottles of blends quite regularly. (Note if you are dealing with them by mail-order: their bottles are glass, so shipping can get heavy. Usually cheaper to buy a larger quantity in a plastic bag and use your own jar to store it.)
As for our most-used:
33rd & Galena: really good on pork.
Trinidad: very nice on grilled fish
Justice: good on root veggies or chicken (mostly onion and garlic in this one)
BBQ of the Americas: we like to mix this into beef burger patties
Fajita seasoning: excellent and not overly salty.
Dried shallots: a lot more convenient than hunting down fresh shallots in recipes that call for them.
Frozen pizza seasoning: if like us, you're not above using a frozen pizza for a quick meal, this blend will make it much more flavorful. I also buy their fennel seed for pizza in general, both frozen and homemade, because I love fennel seed on pizza.
Also, a mention of their baking spices: they have I think 4 different flavors of cinnamon depending on what you prefer, and they have
seriously excellent high-fat cocoa for baking. The vanilla is also very good, if you don't already have access to Nielsen-Massey.