When Paola Santana received a Fulbright scholarship a decade ago, she moved from the Dominican Republic to Washington, D.C., to earn a masters degree in government procurement law. Upon graduation, she anticipated fixing dysfunctional government systems by working in government. Instead, she ended up starting two Silicon Valley startups meant to remedy government shortcomings from the outside in.

Santana launched her latest venture, Social Glass, in San Francisco in 2017 to build software for government workers that makes it easier for them to do their jobs. Its current focus is an online marketplace called Glass Commerce that government buyers use to shop for products ranging from N95 …