Does it overshoot when connecting VBatt without USB power connected?
Just because the regulator doesn't get hot when being backfed does not mean it's okay with being backfed! There are many possible routes for backfeeding to cause a regulator like this to malfunction. The bootstrap circuitry, soft start circuitry, internal error amp, etc could all exhibit problems when starting up while being backfed.
Adding a diode between the output of the regulator and Vcc would be a good idea. There may be other solutions, like changing the way you handle the enable pin, but the diode will almost certainly solve the problem as long as the converter otherwise works.