Shaders are used to give a rendering effect to textures and surfaces in your game.
This can apply to characters, segments, entities, weapons and then you have post processing shader effects which are used for full screen effects such as bloom, depth of field etc.
The best FPSC shaders are made by a member called Bond1 and included in his model packs. He has released the bump / specular shaders for segments and entities for free though.
If you really want to get into FPSC shaders you need to purchase the TGC Dark Shader extension which allows you to edit and create custom versions of all the shaders for your project.
You will also need to have an understanding of how to create the various assets needed for these shaders such as normal maps, specular maps, height maps etc.
It would probably be worth creating a sticky thread with links to where all the best shaders are. Most people probably don't even know half of them exist!