Antivirus programs generally rely on virus signatures to identify threats. That means the firm would have had to have captured, analysed and work out a signature for all viruses - which is near impossible. A firm called Secunia recently did a test of antivirus programs by preloading test machines with viruses. The top contender was Symantec, because it found 64 out of 300 exploits. Yes, the best one found only 64 !
That said, some of the competitors says the test wasn't fair because by preloading viruses and then installing antivirus programs, the test by passes the active protection that some programs have, usually some form of behavioral detection.
But the fact remains that a single signature driven antivirus program cannot be relied on solely to secure a PC. If you suspect that a program could be a virus, you can upload that file to VirusTotal and let them scan it. Virus Total uses approximately 39 antivirus products to scan the file and gives you the results.