The active-particle number density is a key parameter for plasma material processing, space propulsion, and plasma-assisted combustion.The traditional actinometry method focuses on measuring the density of the atoms in the ground state, but there is a lack of an effective optical emission spectroscopy method to measure intra-shell excited-state densities. The latter atoms have chemical selectivity and higher energy, and they can easily change the material morphology as well as the ionization and combustion paths. In this work, we present a novel state-resolved actinometry (SRA) method, supported by a krypton line-ratio method for the electron temperature and density, to measure the number densities of nitrogen atoms in the ground and intra-shell excited states. The SRA method is based on a collisional-radiative model, considering the kinetics of atomic nitrogen and krypton including their excited states. The densities measured by our method are compared with those obtained from a dissociative model in a miniature electron cyclotron resonance plasma (ECR) source. Furthermore, the saturation effect, in which the electron density remains constant due to the microwave propagation in an ECR plasma once the power reaches a certain value, is used to verify the electron density measured by the line-ratio method. An ionization balance model is also presented to examine the measured electron temperature. All the values obtained with the different methods are in good agreement with each other, and hence a set of verified rate coefficient data used in our method can be provided. A novel concept, the "excited-state system", is presented to quickly build an optical diagnostic method based on the analysis of quantum number propensity and selection rules.