It is best to think of this column having two jobs. First, it needs to seek out the largest transaction on each account. The largest transaction may be a Pledge, GIft, Recurring GIft, etc. Second, the column then displays the Received Amount from the largest transaction it found.
If the largest transaction on an account is a pledge, then typically the Received Amount on the pledge entry is set to $0.00. You would only fill in a Received Amount on a pledge entry if the initial payment was made at the same time as the pledge itself. So the Largest Transaction Received column would look at the pledge entry since it is the largest transaction, then return $0.00 into the column on your report.
Most users really want to use the Largest Received Amount column rather than Largest Transaction Received Amount.