You can solve this easily with XPath.
XPath lets you query for nodes in the document in almost any possible combination. To query for the geocode value that is preceded by a valueName element with the content FIPS6, you can use this query:
/alert/info/area/geocode/value[preceding-sibling::valueName = "FIPS6"]
However, the document has a default namespace for the alert element (as indicated by the xmlns attribute). By default, SimpleXml will not be able to access any namespaced nodes in the document via XPath until we tell it the namespace via registerXPathNamespace
and prefix any elements in the query with an arbitrary prefix.
The result of the XPath will be an array containing SimpleXmlElements. When you cast a SimpleXmlElement to string (or use it in a string context), it will return it's nodeValue, which is the values you actually want to combine, so you can simply call implode
on the resulting array to combine the values into a string.
$alert = simplexml_load_file('http://…');
$alert->registerXPathNamespace('a', 'urn:oasis:names:tc:emergency:cap:1.1');
$fipsValues = implode(',', $alert->xpath(
'/a:alert/a:info/a:area/a:geocode/a:value[
preceding-sibling::a:valueName = "FIPS6"
]'
));
print_r($fipsValues); // will contain "001033,001077"