Look at the example called Write Table to XL. I has all of the basic steps required to write a block of data to a new workbook. With minor modification, you can open an existing workbook.
The best way to write to precise cells is by using Named Ranges. In your worksheet, select the cell that you want to write the data to. On the menu, select Insert->Names->Define. Give a name to the cell such as TestCurrent (no spaces allowed). Then in LabVIEW modify the vi Set Cell Value and bypass the Row Col To Range Format vi. You can specify the value for Cell1 using the defined name and write one value to any location on the page.
The main benefit to named ranges, is that they are adjusted automatically when rows or column are inserted or deleted on the page.