Beginning with GP9, Service Pack 3 and GP10, Service Pack 2, you can no longer change the PURCH account at the summary distributions level. It must be changed at the line detail level. This was a design change made to help with matching the value in the inventory account in the General Ledger to the value of inventory in the Inventory module.
This new behavior causes issues when you want to allocate the receipt of a quantity of the same item to multiple accounts. The work-around to this involves entering multiple lines of the same item on the receiving transaction, opening the Item Detail window for each line, and changing the account distribution at the line level.
Transactions>Purchasing>Receivings Transaction Entry
Note the 3 lines, all for the same item. Next, click on the blue expansion arrow to the right of the Item heading.
Change the Purchases account here. Do the same for the remaining lines and you're good to go.
Note that the purchase order does not have to be setup with multiple lines. You can add the additional lines in the receiving transaction.