This is a question that is asked frequently. Here is the answer that will help you in your MSDS training.
Q: We use an electronic MSDS access system. Are there any special training requirements we need to know about?
A: The most important training requirement beyond those listed in the standard would be teaching staff members how to use the electronic system to access the required information (how to launch the program, any login requirements, e.g. a password, how to navigate the system to find the desired document, etc).
According to OSHA Hazard Communication standard (29 CFR 1910.1200), MSDSs must be "readily available," so I wouldn't be surprised if an OSHA inspector asked one of your staff members to demonstrate the use of the system.