We show that Electron Paramagnetic Resonance (EPR) tagged high resolution photoexcitation spectroscopy is a powerful method for the correlation of zero phonon photoluminescence spectra with atomic point defects. Applied to the case of NV centers in 4H-SiC it allows to associate the photoluminescence zero phonon lines (ZPL) at 1243 nm, 1223 nm, 1180 nm, 1176 nm with the (hk, kk, hh, kh) configurations of the NV centers in this material. These results lead to a revision of a previous tentative assignment. Contrary to theoretical predictions, we find that the NV centers in 4H-SiC show a negligible Franck-Condon shift as their ZPL absorption lines are resonant with the ZPL emission lines. The high sub-nanometer energy resolution of this technique allows us further to resolve additional fine structure of the ZPL lines of the axial NV centers which show a doublet structure with a splitting of 0.8 nm. Our results confirm that NV centers in 4H-SiC provide strong competitors for sensing and qubit application due to the shift of their optical transitions into the technology compatible near infrared region and the superior material properties of SiC. Given that single center spin readout will be realized, they are suitable for scalable nanophotonic devices compatible with optical communication network.