A valve assembly in an internal combustion engine fuel system includes a valve member movable within a valve body to contact a valve seat and block fluid communication between first and second passages. The valve seat and valve member each include a multi-layered coating having a harder metal nitride base layer and a softer metal nitride outer layer. The base layer is relatively incompliant to impacts between the valve member and the valve seat, and the outer layer is relatively compliant to the impacts and thereby deformable. Related methodology is disclosed.