Asking about her husband's opinion before asking about hers implies that one feels either A. She is not entitled to (or intelligent enough to have) her own opinion and so had to ask her husband, or B. uninterested in the Secretary of State's opinion. It seems to have gender bias implications; i.e., if the roles were reversed, no one would have asked Bill Clinton about his wife's opinion on a matter of state or international policy.
The Secretary of State of the United States of America is not a mouthpiece for her, admittedly quite popular, husband. When she is at a press conference or interview, it is considered poor taste, if not downright rude, to ignore her opinion and ask for his, especially since his opinion, technically, has little or no relevance to the situation.