basically the material controlls what properties are applied to mesh, whether that be mutliple textures with different ids, or effects and blending. For me, it is easier to assign each material a set of textures (aka diffuse, light, spec maps) for one particular area - i find it less confusing. However it is possible to use one mat, and then add multple textures to it each with a different id and then 'assign' them to certain parts of a mesh via selection. This has the advantage of having one mat to deal with for say one part of a scene versus haveing 24 for just one model.