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And to be honest it should not always succeed. Charisma is no guarantee of success with anyone in reality, no matter how high it may be and I like that it's the same in game.
However, you can take a few personality drugs that might help you be more successful.
Charisma determines the base chance to succeed, with then is randomly determined. But because of how the formula is set up, you can indeed succeed at 100% of the checks all of the time. A Charisma of 11 gives a base chance to succeed of 165%, and the most difficult Speech checks lower that chance by 65%, leaving a 100% chance to succeed.
I usually pass yellows with 3, and some oranges with 6 but not reds.. 10 fails on red sometimes.. very rarely.
Difficulty Level
Yellow -35%
Orange -50%
Red -65%
Example; 6 charisma character (for local leader perks)
Yellow 55%
Orange 40%
Red 25%
9 charisma (wear a +1 CHA hat and +2 CHA suit as a 6 CHA character)
Yellow 100%
Orange 85%
Red 70%
Lady Killer/Black Widow gives situational +10% chance to opposite sex.
There's a magazine (scav 1) in nuka world that gives +10 chance to all.
start with 10, get hungry/thirsty in survival when building in sanctuary, when char is debuffed below 10 consume "you are special" for +1 C , eat/drink, permanent 11, destroyer helm from covenant and we reached 12, later teh bobblehead and we have 13...
From charisma checks to pick pocketing to VATS. You will always have at least a 5% minimum fail chance.
normal armor/clothing stat boosts don't apply in power armor, the only exception is if you enter power armor that doesn't have a helmet the stat boosts from the head and eye slots will apply and the items that give those boosts will be rendered.
note that entering power armor and unequipping the PA helmet will not retroactively apply the stat boosts, you will need to exit and re-enter the PA.