We examine experimentally and computationally the nature of substitution of perylene in polycrystalline solid alkane matrices (Shpol'skii systems). The technique of low temperature excitation-emission matrix spectroscopy is used to determine all substitution sites in alkane matrices from hexane to decane. A theoretical method from the group of Jortner [Shalev , J. Chem. Phys. 95, 3147 (1991)], which was extended and applied by us to this problem in the past [Wallenborn , J. Chem. Phys. 112, 1995 (2000)], allows one to separate the perylene sites in all alkanes into normal and defective sites. Normal sites are obtained by direct substitution of two alkane molecules by a perylene molecule, while defective sites are derived from normal sites by eliminating one of the four nearest neighbors of perylene in the lattice planes parallel to the chromophore. We discuss the strengths and limitations of the present theoretical treatment, which can serve as a valuable supplement and guide to line-narrowing and single-molecule spectroscopic investigations of impurity centers in low-temperature solids.