The best way to EV Registeel is with a specially defensive spread with Calm if you don't use any physical attacking moves, Careful if you aren't using Zap Cannon and have a physical move such as Explosion, or Sassy if you are using Zap Cannon + a physical move like Explosion.
Some viable moves on Registeel include Seismic Toss, Stealth Rock, Thunder Wave, Toxic, Counter, Explosion, Zap Cannon, and occasionally coverage moves such as Shadow Claw/Earthquake/Ice Punch. It's usually less common for Registeel to use a coverage move. People usually want to use the utility moves on Registeel to better take advantage of his ridiculous bulk. I don't use Zap Cannon, but other players like it and have had success with it.
As for a good EV spread, you want to maximize HP, hit a jump point in special defense, and put the rest of the EVs in defense. Attack EVs on Registeel aren't necessary unless you are trying to do something specific with the EVs.
Some example EV spreads with a Calm/Careful/Sassy nature include 252 HP / 4 Def / 252 SpD, 252 HP / 40 Def / 216 SpD, 252 HP / 80 Def / 176 SpD, 252 HP / 120 Def / 136 SpD, 252 HP / 160 Def / 96 SpD, and 252 HP / 200 Def / 56 SpD.
The spread you use depends on how well you want Registeel to tank special attacks or physical attacks. It depends on what your team needs.
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