I have lived in both countries. Chile is the neoliberal poster-boy of the Americas - the country was completely reformed under the Pinochet government . The members of the government in charge of the reform had mostly studied at universities in the US (the so called Chicago Boys). As a result almost everything is privatized today in Chile: healthcare, public transportation, pensions, education (from elementary school to university), large portion of the highways system (and it is expensive), utilities (I paid way more in Chile than in Argentina) etc. etc. A friend of mine is a single mother in the Valparaiso region and she pays a fee every month to some ambulance provider - so in case something happened to her daughter she gets an ambulance coming to her house. Also my impression was that higher education was quite expensive (but not that good) when considering the average income - preventing members of the lower classes from sending their kids to college. There are often mass demonstrations in Chile demanding free education. The pictures of the police beating up the students resemble footages from the time of the military coup.
Regarding the GDP per capita in Chile: Have you looked at the distribution of the income? My impression is that there is a very small very rich upper class (with strong ties to the current center-right/extreme right government and the former Pinochet government) but a lot of poor Chileans and even lower middle class members seem struggling to make it. Also wealth seems to be concentrated in some parts of Santiago (center versus periphery).
Having that said I think it is easier to start a business in Chile. The laws and (less) regulations in Chile are business friendly and consumer protection seems to be very limited. As some have mentioned in another thread there is even a program that gives you (expats!) around $40.000 USD to start up your business (program called "Startup Chile") and you do not have to pay it back. I have met some young entrepreneurs who got the grant - all of them left Chile after finishing the six months of the program.