Hello Everyone. I just upgraded my rig to a whopping 32 gb of ddr3 ram, and was wondering if skyrim will utilize that on it's own or if I need to tweak the ini to help it along. I appreciate any help or advice to achieve this. thanks!!

No, it won't. And no, there isn't. Skyrim is a 32-bit application, so it can only use up to 2³² bytes of RAM. Or, 4GB. No ini tweak can change this.

No one both counts and it's not necessary either.