Thank you Lutz, I did add the namespaces and it returned the correct values;

;with xmlnamespaces(default 'urn:hl7-org:v3')

select Labelid,

LabelXml.value('(/document/title)[1]', 'varchar(50)') AS 'Title',

LabelXml.value('(/document/effectiveTime)[1]/@value', 'varchar(50)') as effectiveTime

My issue now is unfamiliarity with the xml...