Daniel K. Inouye Solar Telescope (DKIST) is designed to deliver accurate spectropolarimetric solar data across a wide wavelength range, covering a large field of view simultaneously using multiple facility instruments for solar disk, limb, and coronal observations. We show successful design and implementation of National Solar Observatory Coudé Laboratory Spectropolarimeter, a custom metrology tool for efficient continuous broadband polarization calibration of the telescope mirrors through a coudé laboratory focus. We compare multiple fitting techniques for the 10 to >140 variable DKIST system polarization models. We compare results with the first DKIST solar calibration observations and find small thermally forced retardance changes of ±0.2  deg and ±0.5  deg for two separate SiO₂ retarders. Modulation matrices derived are stable to <  ±  0.01 per element during the first on-Sun calibration tests. We achieve good fit agreement to our metrology-based model over a 390- to 1600-nm bandpass. The solutions are robust and efficient using only 10 input Stokes vectors from elliptical calibration retarders. We developed a custom polarizer assembly used with metrology tools to orient the DKIST polarization coordinates to better than 0.1-deg clocking angle.