The headphone to RCA jacks might sound fine, but it tends to be my last choice at connecting to a computer.
However, it is always worth a try to see if it sounds good before moving up to a sound card or external DAC.
The items that can make the analog out of a computer problematic: Integrated audio on a mobo may not be the greatest, may need to worry about cable shielding on the headphone to RCA, some computers may have inadequate power supply, and inside a computer is a rather EM noisy area.
For these reasons, I prefer a DAC. A decent shielded sound card can also be fine.
Another good option is if the computer has digi coax or optical, then hook that straight to a receiver. Or a cheaper sound card that has one of those outs.
I can tell you from personal experience that a cheapy Dell desktop sounded like crap using the analog outs to stereo stack, but a ~$30 sound card with optical out fixed that.