The polarization measurement system deals with polarized light-matter interactions, and has been a kind of powerful optical metrology applied in wide fields of physics and material. In this paper, we address several general theoretical aspects related to the system model and optimization for linear polarization systems from a view of the matrix algebra. Based on these theories, we propose a new framework of superachromatic polarization modulator (PM) by combining a linear polarizer and a sequence of parallel linear retarders (LRs) for a typical kind of linear polarization system based on the rotating compensator (RC) principle. In the proposed PM, the LRs are made of quarter-wave plates and as a whole act as the RC. Compared with conventional achromatic/superachromatic composite waveplates, the LR sequence has general axis orientations and is optimized by the condition number of the instrument matrix of the PM, which thereby provide much more flexibility to achieve uniform, stable and complete polarization modulation over ultra-wide spectral range. The intrinsic mechanisms, including the working principle, optimization strategy and in-situ calibration method of the proposed PM, are presented and revealed mathematically by the matrix algebra. Results on several prototypes of the PM demonstrate the validity and capability of the proposed methods for applications in broadband polarization measurement systems. The fabricated PM is further applied to a home-made dual RC Mueller matrix ellipsometer, and the accuracy and precision in the full Mueller matrix measurement are better than 2‰ and 0.6‰ respectively over the ultra-wide spectral range of 200∼1000 nm. Compared with existing techniques, the proposed PM has advantages due to superachromatic performances over ultra-wide spectral ranges, stable and complete modulation of the polarized light, and convenience for adjustment and calibration.