The most important thing about singing a duet, is finding a partner that has a singing voice that blends well with yours. There should be some chemistry between you, that makes singing a love song believable. When you sing to each other, your eyes should meet, and it should show feelings between you both. It is a form of acting and takes practice. If it is not a love song, and sung between two of the same sex, there needs to be a presence about each of you, which reveals feelings such as humor, or friendship, or even a bit of the comic showing though.
A duet is when any two people sing and share a song together, They could be having a humorous time together, or more serious. Make sure that each have solo parts. Unless you try to freestyle harmonize, layer or echo lyrics, do not clash roles, trip up lines, or ‘cross lanes’. That means that if you sing lower than your partner, remain there. The limit would be if you are both singing the same note. Stay consistent.