The correct ambiguity resolution of real-time kinematic precise point positioning (PPP-RTK) plays an essential role in achieving fast, reliable, and high-precision positioning. However, the ambiguity of incorrect fixing will cause poor PPP-RTK positioning performance. Hence, it is essential to optimize the selected strategy of the ambiguity subset to obtain a more reliable ambiguity resolution performance for PPP-RTK. For this reason, a partial ambiguity resolution (PAR) method combining quality control and Schmidt orthogonalization (Gram–Schmidt) is proposed in this study. To investigate the performance of global positioning system (GPS) dual- and three-frequency PPP-RTK comprehensively, the PAR method based on the Gram–Schmidt method was analyzed and compared with the highest elevation angle method, which considered the satellite with the highest elevation angle as the reference satellite. The performance of ambiguity fixing, atmospheric corrections, and positioning were evaluated using five stations in Belgium and its surrounding area. The results showed average epoch fixing rates of 81.01%, 95.92%, 82.05%, and 97.93% in the dual-frequency highest elevation angle (F2-MAX), dual-frequency Gram–Schmidt (F2-ALT), three-frequency highest elevation angle (F3-MAX), and three–frequency Gram–Schmidt (F3-ALT), respectively. In terms of the time to first fix (TTFF), 89.02%, 94.25%, 90.24%, and 95.69% of the single-differenced (SD) narrow lane (NL) ambiguity fell within 3 min in F2-MAX, F2-ALT, F3-MAX, and F3-ALT, respectively. As far as the ionospheric corrections are concerned, the proportion of SD ionospheric residuals within ±0.25 total electron content units (TECU) were 95.08%, 95.93%, 95.68%, and 96.98% for the F2-MAX, F2-ALT, F3-MAX, and F3-ALT, respectively. The centimeter-level accuracy of both the horizontal and vertical positioning errors can be achieved almost instantaneously in F3-ALT. This is attributed to the accurate and reliable SD NL ambiguity fixing based on the Gram–Schmidt approach.