The best way to learn the paths tool is to open your favorite character in Gimp - duplicate the layer.
Now create another transparent new layer to create your first segment on.
Now select the paths tool

and begin tracing around each segment of the character.When you get to the end of the line and want to connect it again press the ctrl key on your keyboard and click the end node.That attaches the entire path together.For each segment create a new layer.When you are done go to your paths dialog Windows/Dockable Dialogs/Paths - for each path you want to outline select the path layer and select Edit/Stroke Path.Do this for each path layer until your entire character is outlined.Then do the coloring with gradients or solid colors.
Hint - Before you outline make sure your foreground color is the color you want (usually black for now).
This color can be changed later but black is much easier to see for now.
Hint 2 - SAVE all your paths do not delete any path layers.You can use them even after the image is saved as a XCF file.
Here is another hint - always stroke the path NOT the selection.
Either create a path and go to Edit/Stroke path OR make a selection go to Select/To path /Edit/Stroke Path.
That way you will get nice unjaggy outlines.

That's sorta the beginners tutorial.There is more, much more to it and you will learn as you go.
The important thing is to have fun and take your time.AND NEVER STROKE THE SELECTION!
I can not emphasize that enough.

Good luck and welcome to Gimp Chat!