Large-scale human social network structure is typically inferred from digital trace samples of online social media platforms or mobile communication data. Instead, here we investigate the social network structure of a complete population, where people are connected by high-quality links sourced from administrative registers of family, household, work, school, and next-door neighbors. We examine this multilayer social opportunity structure through three common concepts in network analysis: degree, closure, and distance. Findings present how particular network layers contribute to presumably universal scale-free and small-world properties of networks. Furthermore, we suggest a novel measure of excess closure and apply this in a life-course perspective to show how the social opportunity structure of individuals varies along age, socio-economic status, and education level.