Kinematically complete experiments were performed on the ionization of a laser-cooled lithium target from different initial states, Li(2s), Li(2p) and Li(1s), by 6 MeV H+ and 1.5 MeV amu-1 O8+ impact. In the measured doubly differential cross sections as a function of electron energy and transverse momentum transfer, a significant initial state dependence is found. Furthermore, comparison to quantum mechanical theory shows surprising discrepancies for Li(2s) and Li(1s) while there is good agreement for the Li(2p) initial state.