chances are that you have GUV or AUV mapping, which means you won’t be able to edit easily. If you plan to edit your maps externally, like in PS, you have to setup your UV’s in a way you can work with them, before painting. Once you start painting, you are married to your UV. changing them afterwards, alters your texture layout.
So you model 1st, then setup your UV’s, then paint your texture. If you skip UV setup, than you are just taking whatever is already assigned. If you are using a polymesh, you can group areas of the mesh into colored area’s. If you do this, GUV can become somewhat human readable, based on the groupings. GUV will try to keep groups together. If the UV’s are still not good enough to edit, you will have to do your UV’s externaly.
once again, you can’t paint on a model that has no UV’s. Although you can paint the vertex’s by using the colorize feature. All non-imported zb objects have UV’s assigned, so you can paint on them right away. Imported DXF objects don’t have any UV’s, and imported OBJ can have UV’s if the object was assigned with them.