Every material has a type. In general, you choose a material type based on what you are trying to model and how accurate (in terms of real-world, physical lighting) you want the model to be.
Your choice of a renderer also affects the materials you can use:
Autodesk Materials are based on the Arch & Design material. Arch & Design is a general-purpose material that also has real-world properties, and a large number of options.
When you grow familiar with mental ray rendering, you might choose to use some of the special-purpose mental ray materials that are also available.
An alternative when you use radiosity is to set up the scene with standard materials, but then apply physical characteristics to them with the Advanced Lighting Override material..