a) I don't know. And for me it would take too much time to find out. Just write a code like that:
$a=mysql_fetch_row($result);
$sum=array_sum($a);//http://de3.php.net/manual/en/function.array-sum.php
arsort($a);//http://de3.php.net/manual/en/function.arsort.php
$max=$a[0];
b) why not? Save a unique ID for each user in your `player_stats` and `player_pics` and select the image from `player_pics