We observe time-resolved and polarization dependent two-, three-, and four-photon transitions from a Ni(111) surface covered with a monolayer of hexagonal boron nitride. The spectra show features due to transitions involving two unoccupied intermediate states: the n=1 image potential state of Ni(111) and a boron nitride-related interface state. We use these transitions in order to track the effects of space-charge on the spectra in view of pump-probe experiments, at high excitations densities. A simple model is presented, which reproduces the measured energy shifts and broadenings in great detail, allowing the ultrafast dynamics and the space-charge effects to be disentangled. Moreover, owing to the high excitation densities an additional particular three-photon transition via both the interface state and a virtual intermediate state could be measured and identified. The polarization-dependent transient of this transition has successfully been simulated, allowing the lifetime of the involved intermediate state to be extracted from the data.