To get representative soil samples, a sampling method was verified for crop fields in the vicinity of abandoned mine sites. Application of appropriate sampling or analytical methods is very important as it affects the costs, time, and accuracy of the refined investigation of soil contamination. Two-time sampling for each crop field was conducted to verify the reproducibility of a zigzag method for soil sampling. The soil analysis using a portable X-ray fluorescence (pXRF) device was conducted to measure concentrations of metal species in soils, and its results were compared to the extracted concentrations by the Korean Standard Test (KST) for soils. As a result, the determination coefficient (R (2)) of linear regression analysis for data obtained by ex situ precise measurement or in situ field screening using pXRF was closely related with the ratio of the extracted concentration by KST to interference-free detection limits (IFDL) of pXRF (designated as KST/IFDL). As the specific metal species had a higher ratio of KST/IFDL, its R (2) was even higher in the field screening tests. However, the slopes of linear regression analysis for most metal species extracted by aqua-regia were close to 1.0 so that extracted concentrations by aqua-regia were similar to the analytical values obtained by pXRF, whereas extraction using a weak acid (0.1 M HCl) had different slopes for soils contaminated with different ranges of concentrations of metal species. Especially Zn showed not only high ratios of KST/IFDL because of aqua regia extraction, but also high determination coefficients. Because of its simple, rapid, and accurate capacities for metal analysis, the pXRF analysis showed high applicability in ex situ precise measurements or in situ field screening of metal analysis. In terms of applicability for regulation, especially in situ pXRF field screening with the zigzag method could be effectively applied to achieve an economical survey by determining hot spots or non-contaminated areas if aqua-regia was applied as the extracting agent in the KST for soils.