You can work with the Meta information stored in Pods through the Pods JSON API (or the Pods REST API, still currently in beta).
https://github.com/pods-framework/pods-json-api
https://github.com/pods-framework/pods-rest-api
It wouldn’t necessarily be a matter of extending Pods but getting your scripts to communicate with other API’s or making sure the data stored in Pods is visible to external APIs.
If you don’t want Pods to work on WordPress content, you’d be talking more about communicating with external tables (separate from WordPress but on the same Database as the WordPress installation); you can do this by enabling ‘Advanced Relationships’ in the Components section, which opens up creating relationships to more tables in the installation.
You might be better off bringing your question to us on our Slack chat so we can get a better idea of what you’re trying to do and how you’re wanting to implement your solution so we can point you in better directions.
http://pods.io/chat/
Slack: podswp.slack.com #support channel
I like the idea of being able to use Pods find() etc with remote entities. It’s a definitely cool thing. At this point, we don’t have any such thing, but your best bet would be to find a way to sync those things via an API into a custom post type, custom taxonomy, or even one of Pods’ Advanced Content Types which is just a table that’s separate from WordPress’ data so it doesn’t clog things up for you if there’s a ton of this data and only a small set of content on your site.
The syncing and the remote data access isn’t built into Pods, but I’d love to explore that area more in the future.