Many-body excitations in X-ray photoemission spectra have been difficult to simulate from first principles. We have recently developed a cumulant-based one-electron Green's function method using the real-time coupled-cluster-singles equation-of-motion approach (RT-EOM-CCS) that provides a general framework for treating these problems. Here we extend this approach to include double excitations in the ground-state energy and in the coupled cluster amplitudes, which have been implemented using subroutines generated by the Tensor Contraction Engine (TCE). As in the case of the singles approximation, RT-EOM-CCSD yields a nonperturbative cumulant form of the Green's function in terms of the time-dependent cluster amplitudes, adding nonlinear corrections to the traditional cumulant forms. The extended approach is applied to the core-hole spectral function for small molecular systems. We find that, when core-optimized basis sets are used, the doubles contributions reduce the mean absolute errors in the core binding energies of the 10e systems from 0.8 to 0.3 eV. They also significantly improve the quasiparticle-satellite gap by reducing its overestimation from about 3-5 to about 0-1 eV in CH4, NH3, and H2O, and also improving the overall shape of the satellite features. Finally, we demonstrate the application of the new implementation to the larger, classical XPS ESCA series of molecules and show that the singles approximation can be paired with a modest basis set to study carbon speciation.