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While you are in college or graduate school, you typically have a unique opportunity to secure an internship with a major government organization, including the FBI, ATF and DEA. Note that the competition for these internships is still very high and the process can be time consuming as you need to obtain security clearance for these positions.
I would recommend combing most of the job pages on all the major government organizations you are interested in, and scope out potential internship opportunities. Due to the lengthy and in-depth nature of security clearances, application times for these internships are earlier than most and strictly enforced.
However, if you really put the time into your cover letter and resume, you increase your chances of obtaining a position. I would argue that college major is not a major consideration, as your past experience and interest in the field has a chance of highlighting you as a solid candidate for a position at an elite government agency.