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It is unclear how he came to be in charge of guarding the Venture clan, but it is possible it was done as a punishment for investigating the 'possible' existence of The Guild of Calamitous Intent shown in the season 3 episode The Invisible Hand of Fate.
The origin of Brock's and Dr. Venture's relationship can be traced back to college, where Brock and Thaddeus were roomates. Not that they ever saw each other. Brock was either too busy playing football or getting laid while 'Rusty' would hang around with his pals playing D&D and doing college work. They never saw each other until the day Brock was expelled for killing a fellow football player. Within ten seconds of meeting, the drunken Samson knocked Rusty's teeth out. The first actual conversation they shared was Brock apologizing for hitting him, then passing along a message that Dr. Venture (Sr.) was dead.
Brock's relationship with Dr. Venture's sons, Hank and Dean is a positive influence in the boy's lives and his own.
Hank Venture can often be found spending time with Brock, when Brock is not performing maintenance, killing someone, going to strip clubs, or spending time with some lady or ladies. Brock is also a mentor to Dean, however, Dean does not share his brother's total adoration of Brock. Dean generally makes more sense than the excitable Hank and that provides common ground with Brock.
Muscular and exceedingly capable physically, Brock's favorite weapon is his knife. Most encounters between Brock and his adversary end with Brock covered in their blood, standing on a pile of mangled bodies. He's also a red belt in judo (which signifies he is at least an 9th dan), he uses the throw Ogoshi which means major hip throw.