The joint density functional theory (JDFT) is applied in the context of the grand canonical Kohn-Sham theory to calculate the global and local softness of pristine and N-substituted graphene structures. A comparison is established between the different theoretical approaches to evaluate total capacitance, revealing that the JDFT approach presents the closest result of this property with experimental data. A model of series capacitors is used to determine the quantum and nonquantum contributions of total capacitance, which enables us to determine the limitations of the rigid band approximation for the studied systems. It is found that global chemical softness is proportional to the total capacitance measured in the experiments, when the geometry relaxation is neglected. In this context, it is possible to obtain quantum and total capacitance (and consequently softness) from an average number of electrons vs applied potential plots and the model of series capacitors. Likewise, the relation of capacitance and softness gives rise to a new definition of local capacitance within the JDFT formalism. The evaluation of global and local softness paves the way to analyze electrochemical surface reactivity as a function of applied potential for a solid-electrolyte interface.