You can also index ARRAY columns, meaning if you need a "tags" feature it's ridiculously easy to implement, no need for additional tables.
There's also PostGIS, which has no MySQL analog, and makes doing actual real-world GIS work possible.
There's also neat stuff like exclusion constraints: http://nathanmlong.com/2016/01/protect-your-data-with-postgr...
And there's the ability to do all kinds of neat geospatial queries with PostGIS - eg "list all properties within X distance from the curvy coastline".
The real knowledge gap would come into things like all the various tactics you need to learn to get MySQL to produce good plans for your queries. PG has a much smarter optimizer which is harder to control - if it does the wrong thing, it's harder to encourage it to do the right thing, and philosophically they don't support query hints. OTOH, worst case in PG is usually much better than worst case on MySQL.