Both are different. Using account key, you'll determine different G/L account for freight/delivery costs. Accrual is only usable if you've purchase account activated.
Sorry, I mixed-up accounting and accrual key. Both the accounting and accrual key is used to be assigned against Freight/ Delivery/Rebate conditions in the Calculation schema. If the Condition marked as accruals, then the system looking for accrual key and G/Account associated with it upon GR posting. If you've activated Purchase accounting at company code level, then the system looking for account key and associated G/L account upon GR posting. Both the keys are mandatory and should not be unique for Purchase accounting. Hope it clarifies you.
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