I’m of course not completely unbiased (see my location), but with 10 days’ time, I think you could do both, on something like 7 days PR, 3 days VI – you’d shop around for whether you’d be better off booking a 3-leg Home-SJU-STT-Home (or reverse order) air ticket, or a roundtrip to SJU or STT and then a local island-hop RT next door in the middle of the trip. and you should leave yourself some time to just rest.
USVI:
The US Virgins have been discussed above – I should add, that Charlotte Amalie (St. Thomas) does have some very interesting cultural history, what with the successive occupiers (it was even DANISH, fer goodness sakes!) and the trading freeport tradition (OK, yes, there will be the temptation to shop). I really dug the Red Fort and the oldest active synagogue under the US flag. St. John, of course, is the one that advertises itself as “eco” touristy and all about “nature” and yes it’s the least developed. Basically you’d use either St. T or St. C as your main inbound-outbound gateway, use local flights between St. T & St. J, and ferry between St. T and St. J.
One last warning: though it’s the “US” VI, they have kept on driving on the left side of the road. So do look twice 
As for my home isle…:
Outside Old SJ, a car is indispensable. And dust off that St. Cristopher medal, this is a race that learned to drive from Manhattan cabbies
and to maintain the roads from the Boston public works department
but at least we drive on the right…
Old-city San Juan, and Ponce on the opposite coast of the island, have cultural history out the proverbial wazoo. Old SJ is has fortifications including two huge forts and a city-guirding wall that are a US National Historic Site and a UN World Heritage Site, great harbor and ocean views from the city walls, ancient churches, small museums of various themes (Book, Pablo Casals, African Heritage, etc), art galleries, government buildings (The Governor’s Palace and Capitol are historic buildings open for tours in daytime – I’m quite fond of the Capitol, where I’ve worked 8 of the last 12 years), public sculptures, the main offices and shops of the Institute of PRican Culture and the Center for Caribbean Studies, all housed in fine architectural examples from the 1520s to the Deco age, it is an absolute must-see (and the best part, the Capitol/Governor’s Palace/Morro Castle triangle is all within walking distance for a healthy person). (BTW cheap way to get pictures of Old SJ from the waterside: take a ride on the ferry to Cataño and back – it’s cheap and you get to cross the harbor)
Ponce is a more 19th-early 20th century old-school city with a smaller and quieter (but also beautiful) historic district around the Plaza, with its own cultural museums and a world-class major Art Museum. Also around Ponce good sites to see are the Conservation Trust’s Hacienda Buena Vista, a restored old-time coffee plantation (reservations req. for English tour last I checked), and the Tibes native archaeological site (nothing on the scale of the sites on the continent, but still worthwhile for history).
For nature exploration, the Biggie in PR is the highland rainforest at El Yunque (“Caribbean National Forest”, to the US Forest Svce., Visitors Center 50 min E of SJ), with trails of various degrees of challenge, through various forest biotope levels.
At the opposite corner of the island, (1hr. W of Ponce) there’s the Guánica Biosphere Reserve arid tropical forest, an extreme contrast of environments.
30 min. E of El Yunque there’s the Reserve at Las Cabezas de San Juan, in Fajardo, also run by the Conservation Trust (reservatiosn, again), which includes paths and lessons around the mangrove ecosystem, a historic lighthouse that was a site for a Spanish-American War diversionary skirmish, and another bioluminescent lagoon. Fajardo is also the gateway point to the aforementioned side-islands of Vieques and Culebra and other minor offshore cays.
If you take the coastal road (PR 187) instead of the highway to/from El Yunque or Fajardo, you’ll drive through the Piñones-Vacía Talega coast, which will give you a good sense of what the area around SJ looked like before they plunked down all those condos and hotels righ at the shore, with impressive beach/ocean views (unless the surf’s so high the road is closed!); plus it’ll give you a chance to eat some roadside food that’s good for the spirit, if not for the cholesterol count, and you’ll be driving through the more culturally “African” part of PR.
Other scenic/photogenic locations that may be of interest include the Reserve at Cabo Rojo (Red Cape, Cap Rouge) with its salt marshes, lighthouse, and seaside cliffs, at the extreme SW end of PR; and the Camuy River Caverns Park and the Arecibo Radio Observatory in the inland North.
Do a search for the names of the islands mentioned and my own or Karl Grenze’s dopernames and you should find earlier threads on the same subject.
And oh, yes: I love our islands and peoples but I’m not gonna lie – it’s not Shangri-La. I applaud travelers like you who do not intend to have themselves isolated from their environs,and want to see what the place really has to offer. Whichever destination is chosen, the rule is the same as for any destination these days: a decent application of common sense goes a long, long way to prevent bad situations when moving through unfamiliar territory.