Not new to modding, but relatively new to Steam. How will modding work for Skyrim with Steam, which is a DRM parasi...program?

Exactly the same as it worked with Fallout 3, New Vegas and Oblivion and Morrowind

Valve worked with the modders to ensure tools like OBSE and FOSE worked with the Steam based exes. There's a couple of extra folders to navigate to get to the data files folder, but you face more hassle with Vista and Win 7s security than with Steam.