Graphene-based electrodes have been widely tested and used in electrochemical double layer capacitors due to their high surface area and electrical conductivity. Nitrogen doping of graphene has recently been demonstrated to significantly enhance capacitance, but the underlying mechanisms remain ambiguous. We present the doping effect on the interfacial capacitance between graphene and [BMIM][PF6] ionic liquid, particularly the relative changes in the double layer and electrode (quantum) capacitances. The electrode capacitance change was evaluated based on density functional theory calculations of doping-induced electronic structure modifications in graphene, while the microstructure and capacitance of the double layers forming near undoped/doped graphene electrodes were calculated using classical molecular dynamics. Our computational study clearly demonstrates that nitrogen doping can lead to significant enhancement in the electrode capacitance as a result of electronic structure modifications while there is virtually no change in the double layer capacitance. This finding sheds some insight into the impact of the chemical and/or mechanical modifications of graphene-like electrodes on supercapacitor performance.