Actually there is no point in using LabVIEW for setting primary key, as suggested by Mike it is created during database table creation....
Just for your information.
For a primary key to work well, the field must uniquely identify each row, never contain an empty or null value, and rarely (ideally, never) change. To set the primary key:
Open the database that you want to modify.
In the Navigation Pane, right click the table in which you want to set the primary key and, on the shortcut menu, click Design View.
TIP If you don't see the Navigation Pane, press F11 to display it.
Select the field or fields that you want to use as the primary key.
To select one field, click the row selector for the field you want.
To select more than one field, hold down CTRL and then click the row selector for each field.
On the Design tab, in the Tools group, click Primary Key.
A key indicator is added to the left of the field or fields that you specify as the primary key.