Purple soils are greatly representative of ecologically fragile soils in southern China, yet the impact of vegetation restoration processes on the nitrogen (N) availability in purple soil ecosystems is still unclear. In this study, the soil nutrient content, available N fractions (including microbial biomass N (MBN), ammonium N (NH4+-N), nitrate N (NO3−-N), and total dissolved N (TDN)), and enzyme activities (including urease (URE), nitrate reductase (NR), and nitrite reductase (NIR)) involved in N mineralization and immobilization were investigated across the three vegetation-restoration measures: Camellia oleifera monoculture, Camellia oleifera ryegrass intercropping, and Camellia oleifera intercropping with weeds. The results showed that the Camellia oleifera monoculture mode considerably enhanced the accumulation and availability of soil N and modified the proportion of available N fractions in arable land situated on purple soil slopes, compared to the intercropping mode, the physical, chemical, and microbiological properties of soil demonstrated more pronounced effects due to the Camellia oleifera monoculture vegetation-restoration measures. However, soil nutrient loss is faster on set-aside land and in crop monocultures, and intercropping restoration measures are more beneficial for soil and water conservation under timely fertilization conditions. The soil URE, NR, and NIR activities and MBN content in the Camellia oleifera monoculture model were significantly higher than in the control check sample. Soil N transformation occurs through the combined influence of chemical and biological processes. The relationships between the activities of the three soil enzymes studied and the contents of various components of soil nutrients and effective N displayed significant differences. Notably, URE had a highly significant positive correlation with TOC. There is a strong positive correlation between NR and TN, NIR and TDN, NO3−-N, and NH4+-N. Our findings suggest that vegetation restoration improved the soil N availability and its enzyme activities in purple soils, making an essential contribution to the restoration and sustainability of purple soil ecosystem functions.