NVIDIA has put together a comprehensive tweak guide for getting the most from Skyrim. The tweaks themselves also apply to AMD GPUs so just because you aren’t running an NVIDIA GPU right now doesn’t mean you should skip checking out the information they’ve posted. Much of the information deals with the settings you find under the options menu, from choosing how you want autosaves to work to how far you should set your draw distance to.
They focus on the effects of the graphical settings for the majority of the article as it will be there that most of the tweaking will be done. Results of combining FXAA and MSAA are covered, both in terms of visual quality and performance impact at several different resolutions. As well, textures and shadow quality are examined in depth, including object detail. There are settings which seem to give you improved visual quality with little to no impact on your frame rate, options such as reflections, anisotropic filtering and actor fade can be turned up without crippling your system.
From there they get into the real tweaks, requiring you to edit .ini files (make a copy first) and become acquainted with the console. The steps to disable V-Sync to uncap your frame rates and ditch the annoying mouse stuttering, increase your field of view and fine tune the shadows of Skyrim are revealed. They also cover the console commands in the game, not just how to turn god mode on and off but also how to teleport, turn off grass and other effects for troubleshooting, setting up batch files that can be run during the game and even the ‘triple q’ quick quit to desktop.