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With FMServer 13, 14 and 15 you can only have one Master and one Worker for WebDirect. However, there is nothing stopping you testing and trying different Masters with the same Worker, or different Workers with the same Master, but when in actual use it's a 1-1 relationship.
If a prospective Worker has had FileMaker Server installed using the "multiple machines" and "this is the worker" options selected (can't remember the exact words, but you'll figure it out!), then you simply link to it using the "Edit Deployment" option in the Admin Console of the Master.
If you want to switch the Worker to a different Master, first you would Edit Deployment on the existing Master to "Single Machine", then Edit Deployment on the new Master to link it to the Worker.
All of this assumes that you have installed the same version of FileMaker Server (including updates) on all of the machines concerned.
And don't forget: you can only have one Master running a given license key at any one time. If a license key is in use, and you try to start up another FileMaker server (Master) on the same LAN with the same License key, the second one will not serve databases - the Database Server process will "see" the other and stop.