I'm not an engineer, but I'm a designer used to think outside the box. I work in the oil industry and know for sure taht safety equipment tends to be cumbersome, uncomfortable and ill-fitting. A steel-toe-cap adopts its shape from the shape of the boot, which is barely good to withstand a few pounds impact, and it's hardness, sharp end and design usually results in an amputation. What I would do is think in terms of mittens or Japanese socks. Instead of layering more material on top, I would insert something like an inverted "T" (or the idea of an "I" beam) between the big toe and the rest of the toes to try to give additional strength to that concave shape to prevent from collapsing and severing the toes, as it usually happens.
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