The lateral Casimir-Polder force between an atom and a corrugated surface should allow one to study experimentally non trivial geometrical effects in quantum vacuum. Here, we derive the theoretical expression of this force in a scattering approach that accounts for the optical properties of the corrugated surface. We show that large corrections to the ``proximity force approximation could be measured using present-day technology with a Bose-Einstein condensate used as a vacuum field sensor.