Methanol (CH$_{3}$OH) is a key complex organic molecule (COM) in the interstellar medium, widely used as a tracer of dense gas and hot molecular cores (HMCs). Using high-resolution ALMA observations from the ATOMS survey, we investigate the excitation and abundance of methanol nuclear spin isomers and their relationship to chemical complexity in massive star-forming cores. We identify 20 methanol transitions, including A- and E-type lines in the v=0 state and E-type lines in the v$_{t}$=1 state, and detect 94 HMC candidates. Rotational temperature analysis under the LTE assumption yields average values of 194 $\pm$ 33 K for CH$_{3}$OH-E v$_{t}$=1, 178 $\pm$ 33 K for CH$_{3}$OH-A v=0, and 75 $\pm$ 33K for CH$_{3}$OH-E v=0. Emission from COMs other than methanol is detected in 87 of the 94 cores, with the CH$_{3}$OH-E v$_{t}$=1 line intensity showing a strong correlation with the channel detection ratio (CDR). These results demonstrate that CH$_{3}$OH-E v$_{t}$=1 lines are reliable tracers of HMCs and chemical complexity, and that the CDR provides a robust indicator of molecular richness. The temperature difference between A- and E-type methanol transitions is driven by anomalously strong J(2,J-2)$-$J(-1,J-1) lines, highlighting the importance of analyzing methanol symmetry types separately.
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