I think I've figured this out (through some discussion with a helpful physicist). Yes, of course it's possible to seal a perfectly smooth surface.
The purpose of roughness in o-ring sealing is twofold:
Retention-- roughness helps o-rings remained retained in their groove or other retention feature via friction.
Stress concentration -- roughness provides local stress concentrations to productproduce a better seal. A perfectly flat surface will seal, but may require higher sealing force than an appropriately rough surface due to lack of local stress concentrations in the o-ring. There is an optimal roughness which is nonzero-- too rough and there's a chance you will have leaks across your sealing surface. Too smooth and you're suboptimal with respect to sealing force.