This paper demonstrates the impact of state-of-the-art instrumental calibration techniques on the precision of arrival times obtained from 9.6 yr of observations of millisecond pulsars using the Murriyang 64 m CSIRO Parkes Radio Telescope. Our study focuses on 21 cm observations of 25 high-priority pulsars that are regularly observed as part of the Parkes Pulsar Timing Array project, including those predicted to be the most susceptible to calibration errors. We employ measurement equation template matching (METM) for instrumental calibration and matrix template matching (MTM) for arrival time estimation, resulting in significantly improved timing residuals with up to a sixfold reduction in white noise compared to arrival times estimated using scalar template matching and conventional calibration based on the ideal feed assumption. The median relative reduction in white noise is 33%, and the maximum absolute reduction is 4.5 μs. For PSR J0437−4715, METM and MTM reduce the best-fit power-law amplitude (2.7σ) and spectral index (1.7σ) of the red noise in the arrival time residuals, which can be tentatively interpreted as mitigation of 1/f noise due to otherwise unmodeled steps in polarimetric response. These findings demonstrate the potential to directly enhance the sensitivity of pulsar timing array experiments through more accurate methods of instrumental calibration and arrival time estimation.