You set the base texture within the nif itself. The path to the relevant block usually looks something like this: NiTriStrips > BSShaderLightingProperty > BSShaderTextureSet An alternative texture can be set in the GECK or via xEdit. Or you can duplicate a mesh and assign another base texture to it, then add the new mesh to the game.
Could it be an issue with your keyboard layout? Also, if you use an ENB, it has its own customisable key for taking screenshots, so that could be a workable alternative.