I have this edmx model (see below) and I would like to add an extra association from Order to Worker *-1 as shown by the red line, problem is, the database has already got lots of data that I don’t want to wipe, is it possible to add do this without recreating the tables?

Simply let EF to create a new database in your development environment and use some database diff. tool to get change script from the old database to a new one. VS 2010 Premium and Ultimate contains this diff. tool and you can even use it directly from EDMX designer if you install Database Generation tools power pack.
Another popular diff tool is for example SQL Compare by RedGate.