When in the tool library dialog; on the left hand side that shows the tool folders. Right click in the empty space and you should see an option pop up like in the image below.
Click on the add Library Folder, and a browse for folder dialog will pop open. path to the network location that you want to store your tool library and create a folder if needed.
Now, that creates a new location in which i can create tool libraries. Now, this same thing needs to be done on the other users computers to where this path is setup in their tool library. This time you won't have to create a folder; just select the one that you already created.
Now, once you do that if you have added any tool libraries or tools into that location then once you link that folder into another users Library then they will automatically see those tools populate inside their library.
Also, if a user is in the library while you are creating a tool and they need to see it. They can either close the tool library and reopen it; or they can right click on the tool folder and select reload.
Hope this is a helpful tip for you guys out there, and keep in mind this is good for both HSMWorks and Inventor HSM.