Edit (January 2015):
Yes, you can add a global secondary index to a DynamoDB table after its creation; see here, under "Global Secondary Indexes on the Fly".
Old Answer (no longer strictly correct):
No, the hash key, range key, and indexes of the table cannot be modified after the table has been created. You can easily add elements that are not hash keys, range keys, or indexed elements after table creation, though.
From the UpdateTable
API docs:
You cannot add, modify or delete indexes using UpdateTable. Indexes can only be defined at table creation time.
To the extent possible, you should really try to anticipate current and future query requirements and design the table and indexes accordingly.
You could always migrate the data to a new table if need be.