This is an interesting question, and hopefully this article will help fill in some backstory on this answer. The current medical view is generally yes, EMS can help strengthen muscle tissue, and repair atrophy, but stimulating neurons isn't a replacement for the physical effects of exorcise.
Think of it like a nail gun: It's faster than a hammer, but you still need to bring in building materials, and flush out waste. Muscles grow from a process of tearing down and rebuilding itself as it flexes to perform work, using hormones, insulin, and lactic acid, among many other things, to create conditions that thicken and strengthen the tissue.
That being said, there's no reason why this character couldn't enhance normal exertions like walking, blinking, and breathing, to strengthen those body parts respectively. Additionally, keep in mind that our thoughts are the result of millions of tiny electrical pathways buzzing around in our heads like rollercoasters. It could be interesting to explore the psychology of this metamorphosis, and how intelligence, reason, compassion, and joy might be affected.