Broadly speaking, both methods identify differences between instances of the same data structure, and if those differences are to the exact same piece of data (e.g. Attribute A has value Yes in one copy and No in the other) you decide which value to keep.
However, as stated in the Resolve Conflicts topic in the Replication section, Replication shows the differences in the MS Access DATABASE TABLES for the two replicas. Baselines show the differences between the current PACKAGE in the MODEL and the Baseline of that package.
As Dermot says, Replication is also only possible with a .EAP file in an Access database, not with a DBMS (which you appear to be using).
Replication shows all the differences between the two instances, including those where the two users have made changes to different pieces of data (Attribute A and Attribute B, for example). I don't think you can filter that comparison. Baselines will let you do that filtering, so that you only list the items of data that have conflicting changes; that is what Simon has outlined.
Basically, Joe and Bob do their edits, Joe takes a Baseline of his, washes Bob's changes over his work, then compares the result with his copy. That shows the conflicts.
With five workers, you'd do that four times, washing the cumulative 'master' of the current model over each person's work in turn and then comparing that with the Baseline of the current person's work.
I hope that helps.