Version 2.5.0.63 of Skype is still entirely unable to handle a proxy server that requires authentication. Trying to log in using this version of Skype, I (still) get:
Failed to sign in: https proxy authentication failed
(Note: no authentication was requested by Skype, not even the use of my proxy Keychain item.)
To use the settings from the Network PrefPane, Skype needs to support at least the same proxy options as Mac OS X itself, and that includes authentication. To support more or fewer, Skype should use its own proxy settings dialog.
Ideally it should support the same methods available in iChat, AIM, Adium, Proteus, etc.