The best way and possibly The One True Way To Learn TiddlyWiki™ is learning by doing.
In other words, you have something you wish to achieve in terms of knowledge management or presentation or data storage, etc... and so you try to model that with the componenents you're given. The basic components being tiddlers. Early on, you might meet System Tiddlers and get a glimpse at what makes TiddlyWiki tick and how to hack the very same stuff yourself.
Other than that, learn about tags (System Tags are quire relevant as well), fields, Wikitext, Widgets, Macros, Filters, plain HTML... all the little cogwheels that you can use to build an engine that propels your very own knowledge enterprise.
It's really hard to suggest a generic discovery path. I would think, the most fruitful ones are those where you have an idea and you figure out all the ways you can accomplish that, perhaps even the best way of them all, eventually. ;-)