As a psychological quality and developmental potential of college students, the accumulation of psychological capital is influenced by a variety of factors. Individuals do not exist in isolation, and their psychological and behavioral changes often depend on the relationships that exist with others. In this paper, from the perspective of cognitive psychology, we intend to introduce the origin, classification, application conditions, and estimation methods of the network autocorrelation model, compare the differences between the conventional linear model and network autocorrelation model in processing relationship data through a simulation study, explore the factors influencing the accumulation of psychological capital of college students, and analyze the internal and external factors influencing the psychological capital of college students through the results of questionnaire survey. The actual role and sensitivity of these factors are explored and analyzed, expecting to provide ideas for the intervention and enhancement of college students’ psychological capital accumulation and to provide certain pedagogical references as well as inspiration for the cultivation of students’ psychological quality.