I agree that this is not a dumb question. My answer is that the boss is wrong.
The voltage rating of any component is based on the ability of its insulation system to prevent current from leaking from an energized internal part to the outside world. Let's change the scenario by saying both the wire and the PVC tube have 300 volt insulation systems. Now impose a voltage of 480V on the wire. That will have enough "pushing ability" to force current through the wire's insulation. Now consider the wire is lying on the bottom of the tube, and the tube is resting on a metal bar. You still have 480V pushing current from the metal wire through whatever insulation it encounters. The resistance of the insulation systems is significant, but the current flow is small. So I don't expect any significant voltage drop through the wire's insulation system. Thus, you now have 480 volts pushing current through the tube towards the metal bar.
I may have this all wrong. It wouldn't be the first time. But I will stand by my opinion that the insulation ratings are not additive.