You're not asking a very simple question here. It sounds like the correct answer is to train users better, but that may not be the right approach.

There are many different ways to look at the issue.

One of the most important questions is who is deciding on the tool set. Some IT deployments look great on paper but when users get to use them, these same tools become too much of a hindrance and get abandoned. At the same time, you don't want to ignore things like safety, security, etc.. so a little hindrance may be necessary.

And if the tools are in fact useful and necessary, what else are the users employing to get their work done without them, and why?

Are you solving more of the trivial problems the users are having at the expense of bigger issues.

Is a corporate revision of procedures etc... a better way to achieve objectives?

These are just some of the immediate thoughts that I get when reading your question. It seems like the time to have monthly user education meetings and start listening.