First things first, I'm not sure there's a $post_type global but pretty sure there is a $post->post_type so you should probably be comparing to that. Secondly, unless you want your child themes to completely override all your CSS files (i.e. not use them even if not overriden) then you should be using get_template_directory_uri() instead of stylesheet directory.
Then, to make sure your stylesheet is included, view the source of the add new portfolio item page and see if your stylesheet is there and that the link is not broken, i.e. it links to the correct CSS file.
Finally, make sure the rules in your stylesheet are not the problem (as @ptriek mentioned above), add a #portfolio-options label { color: red !important; } and remove everything else from the stylesheet, this should turn your portfolio option labels to red. If it works then your stylesheet is fine and the rest is up to its contents :)
Good luck!