You have to add the custom field either via the QuickBooks UI, or with a DataExtDefAdd request before you can add or modify the data contained within it.
<?xml version="1.0" encoding="utf-8"?> <?qbxml version="7.0"?> <QBXML> <QBXMLMsgsRq onError="stopOnError"> <DataExtModRq> <DataExtMod> <OwnerID>0</OwnerID> <DataExtName>MyCustomerNumber</DataExtName> <ListDataExtType>Customer</ListDataExtType> <ListObjRef> <FullName>Keith Palmer</FullName> </ListObjRef> <DataExtValue>1234</DataExtValue> </DataExtMod> </DataExtModRq> </QBXMLMsgsRq> </QBXML>