Rashba spin splitting (RSS) in biased semiconductor quantum wells is investigated theoretically based on the eight-band envelope function model. We find that at large wave vectors, RSS is both nonmonotonic and anisotropic as a function of in-plane wave vector, in contrast to the widely used linear and isotropic model. We derive an analytical expression for RSS, which can correctly reproduce such nonmonotonic behavior at large wave vectors. We also investigate numerically the dependence of RSS on the various band parameters and find that RSS increases with decreasing band gap and subband index, increasing valence band offset, external electric field, and well width. Our analytical expression for RSS provides a satisfactory explanation to all these features.