Ashley Giles, the English Slow Left Arm bowler from Warwickshire was known as the 'king of spin' although not anymore: Warwickshire made several limited edition mugs with that nickname printed on. the problem was that they'd spelled it wrong. instead, it read: Ashley Giles The King of Spain! it is a true story!
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Statistically, it would have to be Muttiah Muralitharan. Say what you want about the guy, but the consistency with which he takes wickets is just something.
Shane Warne is also one of my favourites, for bringing back the lost art of spinning. And the numbers are up there for him too. One reason why Shane could be better than Murali is because he had to share wickets with McDermott, McGrath and co and still end up with a considerable haul. However, Shane failed against the best players of spin - the Indians - while Murali has a good record against them.
Tony Lock, BS Bedi and others from yesteryear are also great spinners. Would be interesting to see if they'd have performed as well in this era or whether Murali / Warne would have succeeded on open pitches!