Chambers recorded her solo album The Captain on Norfolk Island over a few weeks in late 1998 with Nash Chambers producing the album and Bill Chambers on guitar. US country musicians Buddy Miller and Julie Miller added guitars and vocals to four tracks. The Captain was released in 1999 in Australia and in 2000 in the US. Chambers won the 1999 ARIA Award for "Best Country Album" for The Captain and a year later she would win "Best Female Artist". The strong word of mouth would eventually lead to The Captain going double platinum in Australia. The Captain would eventually reach the top 50 of the Billboard country albums in 2001 with Chambers touring the US as support act to Lucinda Williams. Subsequently, she supported Emmylou Harris on her Australian tour. Chambers would receive further exposure when The Captain was played on an episode of HBO's The Sopranos.

Chambers' second album Barricades & Brickwalls was released in late 2001 debuting at #4 in the ARIA album charts. The record really took off in early 2002 with lead single "Not Pretty Enough" going to #1 on the ARIA singles charts. Chambers became the only Australian country artist to have a #1 single and album on the charts in that country simultaneously. Subsequent singles "Million Tears" and "If I Were You" also made the Australian Top 40 singles charts in 2002.