To clean the cart before adding a new product, you can use the following filter:
add_filter( 'woocommerce_add_cart_item_data', 'woo_custom_add_to_cart' );
function woo_custom_add_to_cart( $cart_item_data ) {
global $woocommerce;
$woocommerce->cart->empty_cart();
// Do nothing with the data and return
return $cart_item_data;
}
In that SOen thread (which was where I took the above snippet) you can follow a slightly more in-depth discussion on how to do this, as well as how to limit the number of cart items to just 1 which, in practice, is the same thing.)