We report the selective population of Rb or Cs np ^{2}P_{3/2} (n=5, 6; F=4, 5) hyperfine states by the photodissociation of a transient, alkali-rare gas diatomic molecule. Circularly polarized (σ^{-}), amplified spontaneous emission (ASE) on the D_{2} line of Rb or Cs (780.0 and 852.1nm, respectively) is generated when Rb-Xe or Cs-Xe ground state collision pairs are photoexcited by a σ^{+}-polarized optical field having a wavelength within the D_{2} blue satellite continuum, associated with the B^{2}Σ_{1/2}^{+}←X^{2}Σ_{1/2}^{+} (free←free) transition of the diatomic molecule. The degree of spin polarization of Cs (6p ^{2}P_{3/2}), specifically, is found to be dependent on the interatomic distance (R) at which the excited complex is born, a result attributed to the structure of the B^{2}Σ_{1/2}^{+} state. For Cs-Xe atomic pairs, tuning the wavelength of the optical field from 843 to 848nm varies the degree of circular polarization of the ASE from 63% to almost unity because of the perturbation, in the 5≤R≤6 Å interval, of the ^{2}Σ_{1/2}^{+} potential by a dσ molecular orbital associated with a higher ^{2}Λ electronic state. Monitoring only the Cs 6p ^{2}P_{3/2} spin polarization reveals a previously unobserved interaction of CsXe (B^{2}Σ_{1/2}^{+}) with the lowest vibrational levels of a ^{2}Λ state derived from Cs (5d)+Xe. By inserting a molecular intermediate into the alkali atom excitation mechanism, these experiments realize electronic spin polarization through populating no more than two np ^{2}P_{3/2} hyperfine states, and demonstrate a sensitive spectroscopic probe of R-dependent state-state interactions and their impact on interatomic potentials.