As strategic critical metals, tungsten (W) and tin (Sn) require efficient exploration methods for effective resource development. This study implemented an advanced spread-spectrum induced polarization (SSIP) method in the Xitian mining district of southern China. Through optimized survey system configuration (maximum current electrode spacing of 5200 m, 12-channel acquisition, and five discrete frequency points), we achieved significant advancements: (1) a penetration depth of 1200 m, and (2) three- to five-times higher data acquisition efficiency compared to conventional symmetrical quadrupole arrays. Inversion results of resistivity and chargeability profiles from two parallel survey lines (total length 2.4 km) demonstrated an 85% spatial correlation between resistivity and chargeability anomalies, successfully identifying three mineralized veins. Drill-hole verification confirmed the presence of greisen veins (characterized by low resistivity 3%) and skarn veins (moderate resistivity 150–200 $\mathrm{\Omega }\cdot \mathrm{m}$ and chargeability 1.5–2%). The method exhibits a detection sensitivity of 0.5% chargeability contrast for deep-seated W-Sn polymetallic deposits, providing quantitative technical references for similar deposit exploration.