$proxy = new SoapClient('http://magentohost/api/soap/?wsdl');
$sessionId = $proxy->login('apiUser', 'apiKey');

echo "<pre>";
// create new set
$setName = "New Test Set";
$skeletonId = 4;

$setId = $proxy->call(
    $sessionId,
    "product_attribute_set.create",
    array(
         $setName,
         $skeletonId
    )
);

// Get list
$setList = $proxy->call(
    $sessionId,
    "product_attribute_set.list"
);
echo "Set list:\n";
print_r($setList);

// create group
$groupName = "Test Group";
$groupId = $proxy->call(
    $sessionId,
    "product_attribute_set.groupAdd",
    array(
         $setId,
         $groupName
    )
);

// rename group
$newGroupName = "New Test Group";
$result = $proxy->call(
    $sessionId,
    "product_attribute_set.groupRename",
    array(
         $groupId,
         $newGroupName
    )
);

// add attribute
$attributeId = 83;
$result = $proxy->call(
    $sessionId,
    "product_attribute_set.attributeAdd",
    array(
         $attributeId,
         $setId
    )
);

//remove attribute
$result = $proxy->call(
    $sessionId,
    "product_attribute_set.attributeRemove",
    array(
         $attributeId,
         $setId
    )
);

// remove group
$result = $proxy->call(
    $sessionId,
    "product_attribute_set.groupRemove",
    array(
         $groupId
    )
);

// remove set
$result = $proxy->call(
    $sessionId,
    "product_attribute_set.remove",
    array(
         $setId
    )
);