So write your product, then start monitoring it as you release it to production.
Postgres can track aggregate metrics for queries using the pg_stat_statements extension [1]. You then monitor this periodically to find queries that are slow, then use EXPLAIN ANALYZE [2] to dig in. Make improvements, then reset the statistics for the pg_stat_statements view and wait for a new crop of slow queries to arise.
[1]: https://www.postgresql.org/docs/current/pgstatstatements.htm...
[2]: https://www.postgresql.org/docs/current/using-explain.html
After the data is loaded up, start navigating through the application and it will become evident where improvements need to be made. Tools like Django Debug Toolbar [3] help expose where the bad ORM calls are or also by tailing Postgres log files.
[1] https://github.com/FactoryBoy/factory_boy