Two-dimensional electron liquids (2DELs) have increasing technological relevance for ultrafast electronics and spintronics, yet significant gaps in their fundamental understanding are exemplified on the prototypical SrTiO₃. We correlate the exact SrTiO₃(001) surface structure with distinct 2DELs through combined microscopic angle-resolved photoemission spectroscopy and non-contact atomic force microscopy on truly bulk-terminated surfaces that alleviate structural uncertainties inherent to this long-studied system. The SrO termination is shown to develop a 2DEL following the creation of oxygen vacancies, unlike the intrinsically metallic TiO₂ termination. Differences in degeneracy of the 2DELs, with nearly the same band filling and identical band bending, are assigned to polar distortions of the Ti atoms in combination with spin order, supported with the extraction of fundamental electron-phonon coupling strength. These results not only resolve the ambiguities regarding 2DELs on SrTiO₃ thus far, but also pave the way to manipulating band filling and spin order in oxide 2DELs in general.