The phrase signifies a deep, romantic relationship as much as a legal one. They're much more than just husband and wife; they're best friends.
Pro Tip 2/3
Public Recognition
Introducing a couple as husband and wife acknowledges their marriage publicly. At the party, they were introduced as husband and wife for the first time.
Pro Tip 3/3
Unity
The phrase emphasizes the idea of two people functioning as one unit. As husband and wife, they make all major decisions together.