I don't think you'll be able to change the existing highlighting in Excels row/column headers, but:
To apply this to row 1 and column 1 proceed as follows:
Select the cells in row 1 that you want the colour to appear in, go into conditional formatting and use the formula:
=COLUMN()=CELL("col")
Choose the formatting you want to see, click
OK.
Select the cells in column 1 you want this to apply to, go into conditional formatting and use this formula:
=ROW()=CELL("row")
Choose the formatting you want to see, click
OK.
Finally, right click on that sheets tab and choose View Code, then paste the following where the cursor's flashing:
Code:
Private Sub Worksheet_SelectionChange(ByVal Target As Range)
Calculate
End Sub