If I want to make payment entries for invoices raised in earlier Financial Year i.e. Apr 2013-Mar 2014 in April 2014 is it possible?

Yes, it is possible. Once the new accounting period related to 2014-15 is created, “switch to that accounting period” and then enter the payment details like you have been doing all along.
All you need to ensure is that the payment date is of a date that is on or after 1st April 2014. If the payment belongs to an earlier date, please go to Accounting->Accounting Periods screen and again switch to the 2013-14 period and do the payment entries. Basically the date reflected on the ledger should belong to the accounting period you are in.

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