If your CSS comes from a static file, then as Steve mentioned you want to put it in a static directory and specify it in your app.yaml file. For example, if your CSS files are in a directory called stylesheets:
handlers:
- url: /stylesheets
static_dir: stylesheets
expiration: "180d"
The critical thing to remember with this is that when you upload a new version of your CSS file, you must change the filename because otherwise, visitors to your site will still be using the old cached version instead of your shiny new one. Simply incrementing a number on the end works well.
If your CSS is dynamically generated, then when the request comes in you want to set the caching in the response object's headers. For example, in your request handler you might have something like this:
class GetCSS(webapp.RequestHandler):
def get(self):
# generate the CSS file here, minify it or whatever
# make the CSS cached for 86400s = 1 day
self.response.headers['Cache-Control'] = 'max-age=86400'
self.response.out.write(your_css)