When you want to take orders by telephone (new webshop order) you need to create a new payment method (called "webshop order").
After you selected the customer and added all of the products to the order you have to select the "Payment method" "Webshop order" after clicking on the checkout button.
In the synchronisation settings you can determine for each payment method how it should sync to the webshop.
First create another Payment method and go to Menu -> Import/Export -> Edit source -> Tab "Weborder Status" in order to see the sync settings.