Your XML file has a namespace:
<configuration xmlns="http://schemas.microsoft.com/.NetConfiguration/v2.0">
so you need a namespace manager for SelectSingleNode
(see section “Remarks”):
XPath expressions can include namespaces. Namespace resolution is supported using the XmlNamespaceManager. If the XPath expression includes a prefix, the prefix and namespace URI pair must be added to the XmlNamespaceManager.
Something like this should work:
$ns = New-Object System.Xml.XmlNamespaceManager($WebConfigXml.NameTable)
$ns.AddNamespace("ns", $WebConfigXml.DocumentElement.NamespaceURI)
$node = $WebConfigXml.SelectSingleNode("//ns:add[@key='SiteDomain']", $ns)