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A theoretical model that accounts for fundamental plasma processes leading to the formation and decay of XeCs+ ionic excimers in high-pressure electron-beam-excited Ar/Xe/Cs mixtures was developed. Numerical calculations based on the model were performed. For atmospheric gas mixtures, the model predicts an intrinsic efficiency (energy stored in upper state/energy deposited) of 18%. Model calculations also indicate that while XeCs+ was predominantly formed via the rare-gas ion (Xe+) channel over the entire e-beam duration, the rare-gas metastable (Xe*) channel assumes dominance in the afterglow period.