write below code in {theme}/template/catalog/product/view/addtocart.phtml near Add to Cart button.
<?php
if($_product->getSampleProductId()):
$_price = Mage::getResourceModel('catalog/product')->getAttributeRawValue($_product->getSampleProductId(), 'price', Mage::app()->getStore());
$_formattedPrice = Mage::helper('core')->currency($_price, true, false);
$_buttonTitle = "Order Sample @".$_formattedPrice;
?>
<button type="button" title="<?php echo $_buttonTitle ?>" class="button btn-cart" onclick="setLocation('<?php echo Mage::getUrl('checkout/cart/add/product/'.$_product->getSampleProductId()) ?>')"><span><span><?php echo $_buttonTitle ?></span></span></button>
<?php endif; ?>