I used to travel from the USA to PMI at few times a year for work. It certainly isn't an easy place to get to on SkyTeam. Basically you will arrive into either AMS or CDG. From AMS, you take KL to either BCN or MAD and connect to Air Europa. From CDG you will fly AF to BCN or MAD and connect to Air Europa.

Air Europa has been difficult with seat assignments in my previous journeys. They are not assigned until you check in. On multiple occasions, I would arrive for my Air Europa flight in BCN with my NW/DL boarding pass only to find out I was issues a duplicate seat. Be sure to recheck with Air Europa when you make the connection to save yourself any surprises. Hopefully now that they are more a part of SkyTeam that things will improve. It is a very short flight from BCN to PMI... about 20 minutes on a good day.

BCN is the preferred airport to connect through as the terminal is new, the gates tend to be closer and there is a nice general service lounge in the front that Sky Team Elite Plus members can hang out.