I see that those two compounds mean husband and wife, as a married couple. But is there a difference in usage or context?
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They mean the same thing but 夫妻【fusai】is more polite.
For example, you can use 夫婦【fuufu】to refer to yourselves (私たち夫婦), you can use for others and use it formally (ご夫婦). But you can't use 夫妻【fusai】to refer to yourselves (私たち夫妻 = NG).
Also when speaking formally, ご夫妻 is better than ご夫婦.
夫妻 is the more formal of the two, and shouldn't be used when talking about yourself or people from your inner circle. As a general rule of thumb, use 夫婦 for such close relations or for general comments about married couples, and 夫妻 when talking about people outside your group.
As the other two answers say,
However, since the word