I usually work in layers based on material type for my diffuse maps (ie. Iron, Aluminium, Wood, Rubber, etc. on different layers), so for my specular I just duplicate the diffuse layer sets and hue/sat/brightness/contrast shift them to get approximate base values, then paint highlights on edges or areas of interest, and generally fix up values where they were incorrect.
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specular maps and normal maps
I learned a lot from it.
Also some good info in here...
SciFi Support Beam