The only DME-only navigation I would do is a DME arc, where you know the distance to the station and fly a (say) 10 NM circle around it, not the best way to do XC fliying but used in approaches.
If you have a good map, you could do quick fixes on three DME stations and plot three circles on your map, your position would be in the center of the intersection of the three circles at the time of observation.
All very useless in VFR, just look out of the window and use common sense.