Defeat each player in a single game at least once.
This achievement is actually much simpler than it sounds, and is often accomplished daily in online matches everywhere. First, pick a strong attacker like Yuki or Tomomo, and then just attack other players every chance you get. If you keep this up, by mid to endgame, you'll have scored a kill on everyone at least once, especially if you play on a smaller map like Practice Field with weaker defenders like Marie Poppo. To further expedite this process, try loading attack buff cards like I'm on Fire! or Big Magnum into your deck and possibly a few Pudding to be used sparingly after counterattacks to increase survivability.
If this method is proving too difficult, Kai's first scenario featuring Poppo and two enemy-character players make this achievement a snap, especially on Casual difficulty. Just keep track of who you've already killed and hunt those remaining, and you'll achieve this in no time.