This paper reports experimental results for the influence of target excitation and orbital alignment on the charge exchange process for the systems Ne⁺, Ar⁺-Na(3s, 3p) for impact energies in the 1-15 keV range. The cross section parameters are found to depend sensitively on collision velocity and choice of projectile. Using earlier results by Aumayr et al (Z. Phys. D 6 (1987) 145-153) for the Na(3s) target, the relative cross sections are put on an absolute scale. A strong dependence of the total electron transfer cross section on the target state is observed, most dramatically for low energy Ar⁺ impact for which the cross section for a Na(3p) target is more than 200 times larger than for Na(3s). Time-of-flight spectra show that electron transfer channels with energy defects near zero are strongly preferred. Cross section estimates based on the Demkov-Olson model account well for the major trends observed, but not for the detailed behavior.