i.pca: command not found

Have You tried accessing the binary with the full path?

Maybe Your $PATH variable doesn't contain the default paths? echo $PATH should give something like:

[root@server ~]# echo $PATH
/usr/local/sbin:/usr/local/bin:/sbin:/bin:/usr/sbin:/usr/bin:/root/bin

If it's empty, You may set the PATH variable with this command

export PATH="/usr/local/sbin:/usr/local/bin:/sbin:/bin:/usr/sbin:/usr/bin:/root/bin"

On CentOS possible default full paths are:

/usr/lib64/grass-6.4.4/bin/i.pca - from package: grass

You may install the required package with command yum install {package}

On Debian possible default full paths are:

/usr/lib/grass64/bin/i.pca - from package: grass-core

You may install the required package with command apt-get install {package}
Error in other languages:
i.pca: bevel nie gevind nie
i.pca: comandă negăsită
i.pca: comando não encontrado
i.pca: commande introuvable
i.pca: command not found
i.pca: käsku ei ole
i.pca: không tìm thấy lệnh
i.pca: komanda nerasta
i.pca: Kommando nicht gefunden.
i.pca: kommandot finns inte
i.pca: komut yok
i.pca: nie znaleziono polecenia
i.pca: níor aimsíodh an t-ordú
i.pca: no se encontró la orden
i.pca: no s'ha trobat l'ordre
i.pca: opdracht niet gevonden
i.pca: parancs nem található
i.pca: perintah tidak ditemukan
i.pca: príkaz nenájdený
i.pca: příkaz nenalezen
i.pca: команда не найдена
i.pca: командата не е открита
i.pca: 命令找不到
i.pca: コマンドが見つかりません