The most likely case is that the user has opted out of Klout, or is no longer active on Twitter. We don't report the 'reason' for the 404 so as not to disclose additional information about such a user, or to "scarlet letter" them.
For more information about the potential reasons for a 404 response:
http://klout.com/s/developers/v2#errors
Best practice in the case of receiving a 404 on a "known good Klout ID" or Twitter handle/ID would be to discard the data and requery. It's possible the user becomes active again, re-opts in, or otherwise has data again in the future.