If you can create a column-wise chart, you are halfway there. Just make a standard line chart out of the second column only. Then use ActiveX to change the XValues of the first series to the values of the first column.
In Excel:
ActiveChart.Series(1).XValues = Range(A:A).Value
In LabVIEW:
RefChart to Invoke Node->SeriesCollection
Set Index input to 1
Output SeriesCollection Variant to Variant to Data
Wire type to Excel Series
Output to Property Node->XValues
Change to Write
Convert the array of doubles to Variant
Your chart will automatically become an XY Chart.
Michael
http://www.stitchofclass.com