Completely fine-structure-resolved photoelectron spectra produced from sodium atoms selectively excited into the Na* 2p(6)3p (2)P(1/2) and (2)P(3/2) states were obtained using a third generation synchrotron source in conjunction with laser pumping and high-resolution spectrometry. The spectra show dramatically different behaviors. The strong variations observed in the regions of the Na+ 2p(5)3p (1,3)L(J) photolines and the Na+ 2p(5)4p (1,3)L(J) shakeup satellites are explained within a generalized geometrical model, accounting for the intermediate angular momentum coupling in the ionic states.