Here is an image of the material editor window in 3ds Max. This is the compact version, and is one of the ways that you can create, edit, and assign materials.
The other way to do it is through the slate editor window, which allows you to view the material in a more node based system. Here you can still create, edit, and assign materials to objects.
This shows my making a multi-material in the slate editor window. This is so that I can have lamps with a black outside and a white inside. A color is assigned to each polygonal face depending on its ID number. 1 is black and 2 is white in this case.
This is how you set the ID of the polygonal faces.
End Result.
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