The stacking order in layered transition-metal dichalcogenides (TMDCs) induces variations in the electronic and interlayer couplings. Therefore, controlling the stacking orientations when synthesizing TMDCs is desirable but remains a significant challenge. Here, we developed and showed the growth kinetics of different shapes and stacking orders in as-grown multi-stacked MoS2 crystals and revealed the stacking-order-induced interlayer separations, spin-orbit couplings (SOCs), and symmetry variations. Raman spectra in AA(A...)-stacked crystals demonstrated blueshifted out-of-plane (A(1g)) and in-plane (E-2g(1)) phonon frequencies, representing a greater reduction of the van der Waals gap compared to conventional AB(A.)-stacking. Our observations, together with first-principles calculations, revealed distinct excitonic phenomena due to various stacking orientations. As a result, the photoluminescence emission was improved in the AA(A...)-stacking configuration. Additionally, calculations showed that the valence-band maxima (VBM) at the K point of the AA(A...)-stacking configuration was separated into multiple sub-bands, indicating the presence of stronger SOC. We demonstrated that AA(A...)-stacking emitted an intense second-harmonic signal (SHG) as a fingerprint of the more augmented non-centrosymmetric stacking and enabled SOC-induced splitting at the VBM. We further highlighted the superiority of four-wave mixing-correlated SHG microscopy to quickly resolve the symmetries and multi-domain crystalline phases of differently shaped crystals. Our study based on crystals with different shapes and multiple stacking configurations provides a new avenue for development of future optoelectronic devices.