Electrostatic charge is a major part of modern-day aerosol filtration media (e.g., N95 respirators and surgical facemasks) that has remained poorly understood due to its complicated physics. As such, charging a fibrous material has relied on empiricism in dire need of a mathematical foundation to further advance product design and optimization. In this concern, we have conducted a series of numerical simulations to improve our understanding of how an electrostatically charged fiber captures airborne particles and to quantify how the fiber's dipole orientation impacts its capture efficiency. Special attention was paid to the role of Coulomb and dielectrophoretic forces in the capture of particles of different charge polarities (e.g., particles having a Boltzmann charge distribution). Simulation results were compared with the predictions of the popular empirical correlations from the literature and discussed in detail. Predictions of the empirical correlations better agreed with the simulation results obtained for fibers with a dipole perpendicular to the flow direction rather than for fibers with a dipole parallel to the flow. This indicates that such empirical correlations are more suitable for filters charged via contact electrification (friction charging), where the dipoles are mostly perpendicular to the flow direction, and less suitable for corona-charged media, where the fiber dipoles are generally parallel to the flow direction.