Light dark sectors in thermal contact with the Standard Model naturally produce the observed relic dark matter abundance and are the targets of a broad experimental search program. A key light dark sector model is the pseudo-Dirac fermion with a dark photon mediator. The dynamics of the fermionic excited states are often neglected. We consider scenarios in which a nontrivial abundance of excited states is produced and their subsequent de-excitation yields interesting electromagnetic signals in direct detection experiments. We study three mechanisms of populating the excited state: a primordial excited fraction, a component up-scattered in the sun, and a component up-scattered in the Earth. We find that the fractional abundance of primordial excited states is generically depleted to exponentially small fractions in the early universe. Nonetheless, this abundance can produce observable signals in current dark matter searches. MeV-scale dark matter with thermal cross sections and higher can be probed by down-scattering following excitation in the sun. Up-scatters of GeV-scale dark matter in the Earth can give rise to signals in current and upcoming terrestrial experiments and X-ray observations. We comment on the possible relevance of these scenarios to the recent excess in XENON1T.