I would love to work building highly scalable systems, but I don't get to do it at my current position, and all the job offers out there require having experience doing it. Looks like a chicken-and-egg problem to me.
Normaly a job is not so specific that you can't start into some path like that, and once you are on the path, you can change positions.
But, if your job is that specific, well, that sucks. You'll have to build something on your free time.
And yes, I think typically orgs. today are using SQL Server or Oracle for these databases.
There's this thing I wish existed but AFAIK doesn't: a guide that shows computer people the relative salaries of a bunch of different specialties. So people who have one specialty but would enjoy something else can see what the salaries are like.
Glassdoor is a very rough start on this.
For postgres itself, make sure you know what all the settings in the configuration means, why they make sense 90% of the time and definitely do not make sense in 10% of the time (such as a low memory server with super-fast SSD disk arrays). And in general ofcourse a good knowledge of SQL, index usage/performance. Postgres extensions (arrays, JSON, etc.) are decent, but in my experience it's something you can get into relatively fast if you are solid on the rest.