You just need to make it into a singleton query by plopping some brackets round the selector...
select a.b.value('(PID[sql:variable("@LoopCount")]/PID.3)[1]', 'varchar(200)') as tehvalue2
from @XMLDoc.nodes('HL7Message') as a(b)
...but why are you using a loop? if you explain what you are trying to achieve, maybe we can help get rid of that loop?
MM
select geometry::STGeomFromWKB(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