You can create an observer listening for the checkout_cart_add_product_complete event, and there you can do something like the following
public function addToCartComplete(Varien_Event_Observer $observer) {
$response = $observer->getResponse();
$request = $observer->getRequest();
$response->setRedirect(Mage::getUrl('checkout/onepage'));
Mage::getSingleton('checkout/session')->setNoCartRedirect(true);
}
Your configuration will look something like this:
<frontend>
<events>
<checkout_cart_add_product_complete>
<observers>
<packagename_modulename_observer>
<type>singleton</type>
<class>packagename_modulename/observer</class>
<method>addToCartComplete</method>
</packagename_modulename_observer>
</observers>
</checkout_cart_add_product_complete>
</events>
</frontend>
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