A polarization-aware direction-of-arrival (DoA) detection scheme is conceived that leverages the intrinsic vector sensitivity of a single Rydberg atomic vapor cell to achieve quantum-enhanced angle resolution. Our core idea lies in the fact that the vector nature of an electromagnetic wave is uniquely determined by its orthogonal electric and magnetic field components, both of which can be retrieved by a single Rydberg atomic receiver via electromagnetically induced transparency (EIT)-based spectroscopy. To be specific, in the presence of a static magnetic bias field that defines a stable quantization axis, a pair of sequential EIT measurements is carried out in the same vapor cell. Firstly, the electric-field polarization angle is extracted from the Zeeman-resolved EIT spectrum associated with an electric-dipole transition driven by the radio frequency (RF) field. Within the same experimental cycle, the RF field is then retuned to a magnetic-dipole resonance, producing Zeeman-resolved EIT peaks for decoding the RF magnetic-field orientation. This scheme exhibits a dual yet independent sensitivity on both angles, allowing for precise DoA reconstruction without the need for spatial diversity or phase referencing. Building on this foundation, we derive the quantum Fisher-information matrix (QFIM) and obtain a closed-form quantum Cramér-Rao bound (QCRB) for the joint estimation of polarization and orientation angles. Finally, simulation results spanning various quantum parameters validate the proposed approach and identify optimal operating regimes. With appropriately chosen polarization and magnetic-field geometries, a single vapor cell is expected to achieve sub-0.1$^\circ$ angle resolution at moderate RF-field driving strengths.