Earlier today, I finally realized what a viable skill "Steal" is; however, after making a character whose sole purpose was to level up through stealing, I found that my odds were about the same as my earlier character.

My first character, my regular character, had only 20% steal skill and was able to systematically rob everyone in Shady Sands with some, but not excessive save/load trickery.

My second character, the one made exclusively to be a pickpocket, had 106% steal skill by level 2, but had significantly less success than the first character. Where the first could steal a pistol and caps in one go; the second character is spotted stealing the smallest things and after 12 loads has not been able to take even a single rock -even on easy difficulty, when the other had little difficulty on normal-, despite having five times the skill. Both characters have identical SPECIAL and I cannot understand why this is happening.

Does anyone else have trouble with the "Steal" skill.? Are there any tips/tricks/reasons that 20% somehow has better demonstrably better success than 106%?