Default values can only be assigned to a controlled flex field that is part of a flex field group. Once you have created your controlled field within your group you should see a Default Field Value column to the right of the Field name column; click on the drop-down arrow and select your default term.
As was just explained to me, since ungrouped flex fields do not automatically appear on a record, when you do add one you can chose one of your controlled terms for that particular record.
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