We investigate the asymmetry between electron and hole doping in a 2D Mott insulator and the resulting competition between antiferromagnetism (AFM) and d-wave superconductivity (SC), using variational Monte Carlo calculations for projected wave functions. We find that key features of the T=0 phase diagram, such as critical doping for SC-AFM coexistence and the maximum value of the SC order parameter, are determined by a single parameter eta which characterizes the topology of the ``Fermi surface″ at half filling defined by the bare tight-binding parameters. Our results give insight into why AFM wins for electron doping, while SC is dominant on the hole-doped side. We also suggest using band structure engineering to control the eta parameter for enhancing SC.