It won't hurt your eyes - I use it on my eyelids and under my eyes. I use it all over my face.
I switch back and forth between the Smashbox Photo Finish (the white, oil-free one), the Monistat, Bobbi Brown Vitamin Enriched Face Base and MAC Prep + Prime SPF 50. As you can tell, I NEEDED another primer!
I use the Monistat on days when I think I'll be sweaty. I use the MAC on days when I'll be in the sun. And just randomly use Smashbox and BB.
Smashbox's original Photo Finish is the one with dimethicone. It's the clear one - not the rose, white, lavendar or green one. It's the one you usually get in sample sizes. The consistency of it is the same as the Monistat, but it doesn't dry with the powdery finish, and doesn't prevent oil as well as the Monistat, IMO. Plus it's a LOT more expensive than the Monistat.
Wash your makeup off before bed (I use the Pond's makeup remover towelettes), and you'll be fine - Monistat won't clog your pores if you don't sleep in it.