Congrats in advance on your new reader!
I'm sure you'll get a lot of advice. It's like drinking from a firehose around here.
Personally, I think the Sony Library software is the easiest way to begin. You can download it for free from Sony's web site. Once it's installed, click Sony Store in the left nav pane. That connects you to Sony's store.
In the store, click on Bargain Books to find a bunch of free titles (featured in the middle of the page with covers), and discounted titles.
I'd download some of the free ones just to play around with the software.
Enjoy!
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