Three years ago former teacher Caffari, from Titchfield in Hampshire, sailed around the world in a westerly direction, against the prevailing winds and currents, taking 178 days.
On Monday she made sailing history when she arrived at Les Sables d'Olonne, France, on her 100th day at sea.
Caffari said: "I had an awesome start, then I made a few mistakes tactically in the Atlantic and the intensity of the race in the South Atlantic was just phenomenal.
"I sort of said, 'I'm not sure if I can do this'. I was OK in the south, then I lost a bit of confidence in my first storm.
"Everybody was having lots of problems and that was when all the damage was happening and there was Elies Yann's injury, and I lost all my confidence then."
Thompson was delighted to finish the race one place ahead of Caffari after encountering problems with his yacht.
"I've been fighting to stay ahead of Dee the whole time and keeping my keel problem a secret, and last night the ram broke, and disengaged from the keel," he said.
British sailor "elated" with Vendee fifth place
"I'm amazed I've done any sailing at all, because every day I spent my whole time down below fixing various things, electronics, weather equipment...
"Twenty minutes before I crossed the finish line I thought, 'I've only got to do one tack, nothing can go wrong now', and just had a beautiful crossing of the line.
"I had a few problems in the bow, but I managed to pull up the repairs. The worst thing was getting stuck up the mast on Christmas Day, that was very rough, bumpy and not Christmasy at all.
"Fifth is an excellent result overall, I'm quite happy about that. I wanted to be in the top five, but I hadn't expected the race to be such a race of attrition. But that's pretty good out of 30 boats."
Despite finishing on Saturday, over two days ahead of Marc Guillemot, Davies was denied third spot because the Frenchman had time in hand from helping a stricken rival earlier in the race.
Sam Davies' epic voyage
The Portsmouth born 34-year-old, along with Caffari one of the two women competing in the gruelling race, finished in a time of 95 days, four hours and 39 minutes.
She had 32 hours time redress for diverting to the aid of stricken rival Elies, while Guillemot was granted 50 hours more for his role in the rescue of Elies.
The Frenchman crossed the line at 0121 GMT on Monday, with 0241 GMT the target he had to beat to deny Davies a place in the top three.
Davies's time, achieved in 60-foot yacht Roxy, made her the second fastest female competitor after compatriot Ellen MacArthur, who finished second in 2001.
The four-yearly race was won by Frenchman Michel Desjoyeaux, who finished on 1 February after sailing 28,303.2 nautical miles in 84 days.
Compatriot Armel Le Cleac'h came second after 89 days at sea, while another Frenchman, 2005 winner Vincent Riou, was credited with joint third after his yacht lost its mast during the rescue of Jean Le Cam off Cape Horn.
Thirty yachts entered the endurance race back in November, but just 11 look set to complete the course.
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