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The list was created for young people seeking certain certain service awards, but the reality is that any adult that undertakes such a project successfully - and has the photos, media coverage, blogs and letters of endorsement to prove the activity happened/is happening - is going to get the attention of a humanitarian organization that sees your CV.
For citizens of the USA: Ameri Corps VISTA is the American national service program designed specifically to fight poverty.
The UN brings in international people for jobs when there is expertise needed that cannot be found among local people, when local people are under too much risk to fulfill such a role, such as after a profound disaster or long-term conflict, or when someone who will be seen as neutral is needed in a role.
International candidates must have the exact area of specialization needed for a job.
Also, follow the application process for that job exactly - people that don't follow the process exactly are often tossed right out of the consideration process without senior staff ever seeing their credentials.
Of course, the UN and other international agencies do hire people from developed countries, including Europe, Canada, the USA, Australia, Scandinavia, etc.
Some can be explored or enhanced via online courses for humanitarian workers listed at Relief Web.
If you are from a developing country, you will have an advantage over other candidates from a developed country IF you also have the exact skills and experience needed for a role.
If you do not have the exact match of skills and experience asked for in a job, you are NOT going to be interviewed.
If the job posting says, "fluency in French", then the hiring company wants applicants who can do the job interview entirely in French, not someone who has had a few years of French classes.
If they job says you must know how to communicate in religiously conservative communities, and your CV doesn't say explicitly that you have done that somewhere, you aren't going to be interviewed.
If you have the expertise asked for in a job posting, what will increase your chances to be interviewed?