By combining a pulsed laser ablation vanadium atom (V) beam source with the two-color laser sequential electric field pulse scheme for pulse field ionization-photoion (PFI-PI) detection, we have developed a quantum spin-orbit state selected transition metal ion source for ion-molecule reaction studies. As a demonstration, we show that the V+ ion can be prepared in the single spin-orbit levels of its three lowest quantum electronic states, V+[a(5)D(J) (J = 0-4), a(5)F(J) (J = 1-5), and a(3)F(J) (J = 2-4)], achieving laboratory kinetic energy (E-lab) resolutions of <= 0.2 eV. The precursor V atom beam is first excited to high-n Rydberg states by resonance-enhanced visible ultraviolet laser photoexcitation via the V*[3d(3)(F-4) 4s4p (P-3 degrees)] neutral intermediate state. The total photon energy is tuned in the regions from 54 380 to 63 520 cm(-1) to cover the photoionization energies for the formation of these spin-orbit states. Sharp Rydberg transitions converging to the V+[a(5)D(J) (J = 1 and 2)] spin-orbit levels are identified in the respective PFI-PI spectra for the V+[a(5)D(J) (J = 0 and 1)] states. The analysis of these Rydberg members observed yields an ionization energy of 54 412.65 +/- 0.15 cm(-1) for V atom, which is in excellent accord with the literature value of 54 413 +/- 1 cm(-1) eV. In order to understand the profile for the PFI-PI spectrum of V+ ion observed and thus obtain reliable Stark shift corrections by using the sequential PFI-PI detection scheme, we have also examined the PFI-PI spectrum for Ar+(P-2(3/2)) in detail by varying the retarding as well as the PFI electric field pulses.