If I get what you're saying, yes. In the UVTE: Image > Shade UVs. Blue means it's normals are correct, red is normals wrong way.

Or do you mean how to determine which face is which? In which case you can use the 3D paint tool to sketch rough guides or identifiers, just create a new material, open the 3D paint tool option and Assign/Edit Textures, then Save Texture somewhere where you can open in PS and make the proper texture. Hope that make sense.