Radioimmunoasssay (RIA) is more accurate, but has some risks (radioactive materials), need special lab and licence. ELISA is less accurate but more available. There are other factors might play roles for the accuracy, for example: source of Kit (company), technique, experience, instruments in your lab (automatic pipettes, reader).
for estimation of steroid hormone one can go for ELISA .it would be better option and kits are available easily .Another method you can try HPLC ( High performance liquid chromatography ) . it would give both quantitative and qualitative result.read some research papers related to steroid hormone analysis too.it may help you.
This depends on the biologic matrix, the sensitivity of the measurement you want to get, and the origin of the sample (human, animal, other...). Personally, I believe that the best choice stays mass spectrometry, but after a preliminary step of purification.
Steroids measurements are really very complex. If you only need the measures for a particular experiment, I recommend you to use elisa kits. You can save a lot of time and effort. But if you wish to know more, I recommend HPLC.
If you mean specific, than definitely LC-MS/MS. Depending on the matrix, you will need to extract the target steroids and clean up the extract. With the right method, you will be able to quantify multiple steroids in the same run.
If you do not have access to LC-MS/MS, than commercial ELISA kits can do a good job if you choose a kit with low cross reactivity to other steroids. Antibody based assays (whether RIA or ELISA) are as good as their antibody is, so carefully read the manufacturers' data.