The multiband envelope-function formalism---of which a convenient, analytical formulation is presented---is used to investigate the energies and wave functions of valence-band levels in spherical nanocrystallites of several III-V and II-VI compound semiconductors with finite spin-orbit splitting energy \ensuremath{\Delta}. Interband absorption spectra are deduced. A significant influence of the split-off band is found even in cases where \ensuremath{\Delta} is large, as for CdTe. In fact, \ensuremath{\Delta} is not a decisive criterion for the strength of couplings; Luttinger parameters play a major role. Numerical results are presented for size-distributed crystallites of various binaries (CdTe, CdSe, CdS, GaAs, InP). These are analyzed in terms of the accuracy of measuring the sizes from absorption spectra by using a fitting procedure, and of performing size-selective excitation of photoluminescence. It is also found that optical transitions between the ground valence- and conduction-band levels may be forbidden, due to incompatible symmetries. Calculations neglecting the influence of the split-off band are unable to account for this property, which strongly affects photoluminescence mechanisms. \textcopyright{} 1996 The American Physical Society.