One can use different methods like invasive and non-invasive methods for the determination of steroid hormones. However, recently scientists have shifted to non-invasive methods such as determining steroid hormone concentrations in wild populations using either urine or fecal samples.
It depends what are your aims. In human populations, except RIA (radioimmunological) and ELISA methods, recommendations are shifting now to the usage of combination of liquid chromatography/mass spectrometry. They are expensive but much more precise, especially in menopause. For that read please f.e. recent papers of Prof. R.Santen and Prof. M.Dowsett.
RIA is accurate method, but need precaution and especial Lab. ELISA is less accurate but widely available and need any precaution. Electrochemiluminescence immunoassay (ECLIA) using Cobas e 411 immunoassay analysers (Cobas®, Roche Diagnostics BmbH, Mannheim, REF 05200067 190) is mostly accurate, but need huge lab.
There are several validated methods on the EPA and ICCVAM web site ranging from cell based to ELISA to in vivo. Most have been through some or complete validation. Several are available to researchers at little or no cost. I would start there and determine which method fits your needs most.