You can order via this site or via the post through your usual stone-age ordering system.
1) Don’t forget your official order number from your finance officer or bursar where necessary.
2) You can pay via cheque in the post in advance, or if you are a school or college with a reputable record of payment - by invoice with payment later by cheque or BACS.
3) Actually, payment to an invoice is the normal method of payment if you have any sense - since it always costs more to pay by other means. So if you are a school / college / library / institution (including a prison), order over this site, and wait for the invoice with the goods.
4) But, if you are an individual and are buying resources without any approval to spend from your school or college - please pay up front via cheque.