Total hours is a good measure of skill, but perhaps not the best measure of skill. That is usually attributed to hours on type. Also important to note that, at least for this answer, I'm conflating "skill" with "lack of accidents". That's not necessarily a good measure of skill.
Back in 2013, Aviation Safety magazine posted a good piece on exactly this subject. Some relevant excerpts:
In 2010, 96 percent of the 1500 civilian aircraft accidents in the U.S. involved general aviation. According to the NTSB’s 2010 Annual Review of Civilian Aircraft Accident Data, the average pilot pursuing personal flying and who was involved in an accident had a “total flight time of 2863 total hours, with a range of 20 to 31,270 hours. The average time in the type of accident aircraft was 460 hours, with a range of 1 to 10,000 hours.”
Anybody with even a modest grounding in statistics can see a standard deviation and data variance big enough to fly a Twin Beech through.
So clearly, pilots of all skill levels measured by "total hours" have accidents.
A 2002 epidemiological study of airline pilots by researchers at Johns Hopkins University found experience, measured by total flight time, offered a significant protective effect. With adjustment for age, Part 121 airline pilots with 5000 to 10,000 hours had a 57-percent lower risk of a crash than pilots with less than 5000 hours
Total flight time shows significant reduction in accident rates, however insurance rates tell the real story, as these are the people who have actuarial reasons to calculate risk factors.
Based on writings and policies of the aviation insurance industry, pilot experience in a specific aircraft make and model is considered a better measure of competency than total flight time. Insurance underwriters can favorably rank a 1000-hour pilot with 500 hours in the make and model with a 10,000-hour pilot who has no make and model experience.