If your data is strongly interrelated (customers, orders, products, invoices, stock) and you need to query it along varied axes, the relational model is the most natural. Joins, integrity constraints and multi-table transactions are at the heart of PostgreSQL.
If your data consists of self-contained objects with variable structure (profiles, events, heterogeneous catalogues, content), the document model avoids multiplying tables and schema migrations. MongoDB also lets you validate a schema per collection when rigour becomes necessary.
Note that PostgreSQL handles semi-structured data very well thanks to the JSONB type, which is indexable and queryable. For many projects, a relational database with a few JSONB columns covers the need for flexibility without giving up relational guarantees or adding a second engine.