Set a cookie on every user's visit on your site, If the client has that cookie it means he has already visited your site else he has'nt or it could be also checked by IP
A quick script using Cookies:
if(isset($_COOKIE["user_visited"]))
{
//He has already visited you.
}else{
//Set a new cookie.
setcookie("user_visited","user");
}
IP Method
//Need to create a user_ip table for it and store everybodies ip(s) in it.
$user_ip = $_SERVER["REMOTE_ADDR"];
if(isset($user_ip)){
$query = mysql_query("SELECT * FROM `user_ip` WHERE `ip`='$user_ip'");
$count = mysql_num_rows($query);
if($count > 0){
//User already visited you
}else{
//He hasn't visited you.
//Save his IP to know if he visit again.
$query("INSERT INTO `user_ip` VALUES('$user_ip')");
}
}